WO2021046707A1 - Separator plate for fuel cell, manufacturing method, and fuel cell using separator plate - Google Patents

Separator plate for fuel cell, manufacturing method, and fuel cell using separator plate Download PDF

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Publication number
WO2021046707A1
WO2021046707A1 PCT/CN2019/105090 CN2019105090W WO2021046707A1 WO 2021046707 A1 WO2021046707 A1 WO 2021046707A1 CN 2019105090 W CN2019105090 W CN 2019105090W WO 2021046707 A1 WO2021046707 A1 WO 2021046707A1
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Prior art keywords
separator
flow path
fuel cell
substrate
layer
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PCT/CN2019/105090
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French (fr)
Chinese (zh)
Inventor
程建华
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上海旭济动力科技有限公司
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Application filed by 上海旭济动力科技有限公司 filed Critical 上海旭济动力科技有限公司
Priority to CN201980099646.0A priority Critical patent/CN114303264A/en
Priority to PCT/CN2019/105090 priority patent/WO2021046707A1/en
Publication of WO2021046707A1 publication Critical patent/WO2021046707A1/en

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a fuel cell separator, in particular to a fuel cell separator with a cooling medium flow path attached (Adhere) between two base materials as a conductive flexible membrane material.
  • This separator can be used for Solid polymer fuel cell.
  • Fuel cells are generally used in a fuel cell stack constructed by connecting multiple fuel cell units in series.
  • the assembly device is used to assemble the fuel cell stack by stacking components such as end plates, current collector plates, insulating plates, separators, and electrolyte membrane assemblies while properly positioned.
  • a solid polymer fuel cell using a hydrogen ion-permeable solid polymer electrolyte membrane is known.
  • a single cell of a solid polymer fuel cell includes a pair of gas diffusion layers sandwiching a polymer membrane, and separators are arranged on the outside of each gas diffusion layer.
  • the separator in the component parts of the polymer electrolyte fuel cell is formed of a conductive plate-shaped member.
  • An oxidizing gas flow path, a fuel gas flow path, and a cooling medium flow path are formed on the separator. Specifically, an oxidizing gas flow path or a fuel gas flow path is formed on one surface of the separator.
  • the cooling medium flow path is formed on the other surface of the partition.
  • the fuel cell separator in which a plurality of battery cells are stacked and fastened to form a stack is composed of two plate-shaped members joined together.
  • a fuel gas flow path is formed on the outer surface of one plate-shaped member, and an oxidizing gas flow path is formed on the outer surface of the other plate-shaped member.
  • a cooling medium flow path is formed on the inner surface located inside the two plate-shaped members to be joined.
  • the separator has a role as a partition wall separating a single battery cell from a single battery cell, and has the following functions: that is, a conductor that transmits the generated electrons, provides air and hydrogen, and discharges the flow of water or gas. road.
  • a separator In order to make a solid polymer fuel cell practical, it is necessary to use a separator with sufficient conductivity and excellent thermal conductivity that can release reaction heat to the outside.
  • thinner and lighter partitions are required.
  • the separator since the thickness of the separator will increase the internal resistance, the separator cannot be too thick.
  • the mainstream trend is to form a metal separator with a groove-shaped fluid guide flow path on the metal surface.
  • the separator in order to form a flow path on its surface, the separator itself includes the steps of forming the separator itself, such as metal pressing, metal cutting, and The process of repairing the shape of the separator and removing contaminants, the surface film forming process and other manufacturing processes are numerous, and the production cost is high.
  • metal substrates are harder materials that are difficult to mold, so the production time of a single product (Tact time) is increased.
  • Metal has the following problems: metal processing requires expensive equipment investment, high cost, and high material cost, and its processing requires a long step, and it is prone to breakage, wrinkles or bending deformation, etc., and lacks material flexibility, etc. .
  • the resin separator proposed in Patent Document 2 a composite flexible film material is laminated on both sides of a conductive resin plate.
  • the resin separator proposed here is chemically more stable and excellent in corrosion resistance, and is excellent in processability.
  • the contact resistance value is higher, and therefore the conductivity is poor.
  • heat is transferred by vibration, and therefore shows a thermal conductivity that is several orders of magnitude lower than that of metal. In other words, in order to allow electrons to move smoothly, it is necessary to improve the conductivity of the resin separator, and it is also required to improve its thermal conductivity.
  • Patent Document 1 Japanese Patent Laid-Open No. 2006-294335
  • Patent Document 2 Japanese Patent Laid-Open No. 2016-119181
  • the resin separator disclosed in Patent Document 2 has insufficient electrical conductivity and thermal conductivity, and there is room for improvement from the viewpoint of improving electrical characteristics and thermal characteristics.
  • the metal separator of Patent Document 1 has superior electrical conductivity compared to the resin separator of Patent Document 2, but in order to prevent corrosion due to water generated after a chemical reaction, it is necessary to form a passivation coating for the problem of metal corrosion. Etc. to improve the corrosion resistance of the metal separator.
  • Metal separators are relatively thinner than resin separators, but both need to be thinner to increase power density.
  • a roll-to-roll production method is difficult to be applied to an integrated metal separator that is press-formed or imprinted on a fluid guiding flow path.
  • One of the objects of the present invention is to provide a separator for a fuel cell, which can maintain sufficient rigidity and is thinner than a metal separator.
  • the separator has excellent electrical conductivity, thermal conductivity, gas impermeability, corrosion resistance, and low contact resistance.
  • the present invention also provides a method for manufacturing the fuel cell separator and a fuel cell using the separator, thereby improving the power generation performance of the fuel cell, reducing the thickness of a single cell, and contributing to the realization of high power density of the fuel cell , Miniaturization or light weight, can improve operability with good processability, and can be produced at low cost in roll-to-roll mode to meet market demand.
  • One aspect of the present invention uses materials that can impart electrical conductivity, thermal conductivity, gas impermeability, corrosion resistance, rigidity, reinforcement, and flexibility to form the separator, so that the fuel cell has the above characteristics while improving the power generation performance of the fuel cell (High output power volume density, high output power weight density, higher reliability).
  • one aspect of the present invention is formed on a flexible substrate (flexible film) that has sufficient electrical conductivity/thermal conductivity, airtightness/corrosion resistance, and is easy to process.
  • the fluid guides the flow path, thereby providing a separator having conductivity, thermal conductivity, gas impermeability, corrosion resistance, rigidity, reinforcement, and flexibility, and a solid polymer fuel cell using the separator.
  • the object of the present invention is to cope with the high power density and miniaturization/weight reduction of fuel cells, and to realize the structure of fuel cell separators with extremely thin thickness and flexibility (easy to process, hard to concentrate stress, and improved reliability). , And can use low-cost roll-to-roll method for mass production.
  • the present invention provides a separator for a fuel cell constructed in the following manner.
  • One aspect of the present invention provides a separator for a fuel cell, comprising a pair of separator substrates arranged oppositely, the separator substrate being a conductive carbon composite flexible membrane material; and the separator is arranged on the pair of separators The cooling medium flow path between the substrates.
  • it further includes a reactive gas flow path arranged on the outer side of the separator substrate.
  • it further includes a surface treatment layer and/or a surface modification layer covering the surface of the separator substrate and having at least one of the following characteristics: surface corrosion resistance, interface adhesion, and interface adhesion.
  • it further includes a strengthening layer for increasing rigidity covering the surface treatment layer and/or the surface modification layer.
  • the cooling medium flow path is formed on the separator substrate, the surface treatment layer, the surface modification layer, or the reinforcement layer.
  • it further includes a reactive gas flow path arranged on the outside of the separator substrate, the reactive gas flow path being formed on at least one of the separator substrates, on the surface treatment layer, On the surface modification layer or on the strengthening layer.
  • the separator substrate includes at least one conductive material and at least one resin composition.
  • the separator substrate further includes at least one conductivity enhancing material.
  • the conductive reinforcing material includes fine graphite fibers, carbon nanotubes and/or graphene.
  • the conductive reinforcing material is arranged perpendicular to the extension surface of the separator substrate or arranged obliquely with respect to the extension surface of the separator substrate.
  • the attachment material of the cooling medium flow path and/or the reaction gas flow path includes a dense carbon-based material and/or a porous carbon-based material.
  • a hydrophilic coating solution, a hydrophobic coating solution, or a water-repellent coating solution is attached to all or a partial area of the reaction gas flow path, or only in the channel portion of the reaction gas flow path.
  • Hydrophilic coating solution is attached to the bottom of the tube.
  • the thickness of the separator substrate is in the range of 10 to 200 ⁇ m.
  • the thickness of the surface treatment layer is in the range of 1 to 1,000 nm.
  • the thickness of the surface modification layer is in the range of 0.1 to 1,000 nm.
  • the thickness of the strengthening layer is in the range of 1-50 ⁇ m.
  • the height of the cooling medium flow path and/or the reaction gas flow path is in the range of 1 to 500 ⁇ m.
  • the thickness of the separator is in the range of 10 to 1,000 ⁇ m.
  • the present invention also provides a fuel cell, including a plurality of membrane electrode assemblies and a plurality of separators as described above, each membrane electrode assembly being arranged between adjacent separators.
  • the membrane electrode assembly includes a catalyst coating film and gas diffusion layers respectively provided on the first side and the second side of the catalyst coating film.
  • a reactive gas flow path is arranged on the side of the separator substrate and/or the side of the gas diffusion layer opposite to the separator substrate.
  • the present invention also provides a method for manufacturing a separator for a fuel cell, which includes the following steps: providing a pair of separator substrates as conductive carbon composite flexible membrane materials; at least one separator of the pair of separator substrates A cooling medium flow path is attached to one side of the plate base material; the pair of separator base materials are bonded together, wherein the cooling medium flow path is located between the pair of separator base materials.
  • the method further includes pressurizing and/or heating the pair of separator substrates.
  • it further includes forming a surface treatment layer and/or a surface modification layer on the surface of at least one separator substrate of the pair of separator substrates, the surface treatment layer and/or surface modification
  • the layer has at least one of the following characteristics: surface corrosion resistance, interface adhesion, and interface adhesion.
  • the method further includes forming a reinforcing layer for improving rigidity on the surface of at least one separator substrate of the pair of separator substrates.
  • it further includes a reaction gas flow path attached to the non-bonding side of at least one separator substrate of the pair of separator substrates.
  • the method further includes coating a hydrophilic coating liquid or a waterproof coating liquid on all or a partial area of the reaction gas flow path.
  • a method of providing the pair of separator substrates includes: laminating a conductive material, a conductive reinforcing material, and a resin composition to form a laminated body; covering the laminated body with a film having elasticity; adding The laminate is pressed and/or heated to harden the laminate.
  • the material of the surface treatment layer includes: the same material as that of the ribs constituting the cooling medium flow path; or the total content of carbon component is from the side of the separator substrate The material of the inclined functional structure that the outer side becomes higher.
  • the attachment material of the cooling medium flow path and/or the reaction gas flow path includes a first material and a second material that are entangled with each other, and the first material includes fine carbon fibers, carbon nanotubes, and graphene. Or a combination thereof, the second material includes a conductive resin. .
  • the attachment method of the cooling medium flow path and/or the reaction gas flow path includes coating, printing, glue dispensing, spraying and transfer printing.
  • the present invention provides a separator for a fuel cell.
  • the separator uses a sheet-like structure with improved electrical conductivity/thermal conductivity as a base substrate, and a cooling element with improved electrical conductivity/thermal conductivity is formed on one surface of the substrate.
  • the medium flow path and/or the reaction gas flow path with improved electrical conductivity/thermal conductivity is formed on the other surface of the substrate, thereby achieving high electrical conductivity, high thermal conductivity, high output volume density and high output of the fuel cell Power weight density.
  • the use of non-corrosive functional materials to attach the fluid guiding flow path to the surface of the substrate can ensure the entire conductive path and heat dissipation path of the fuel cell stack and help prevent corrosion from developing.
  • the separator can be made rigid and strengthened. Furthermore, by using a thinner base material, the thickness of a single fuel cell unit can be suppressed, and the stacking interval (cell pitch) of the fuel cell stack can be shortened. Compared with stacks using metal separators, it can achieve thinner/lighter weight, and obtain a fuel cell with high output power volume density and high output power weight density.
  • the present invention utilizes a conductive/thermal conductive substrate and a functional material providing conductivity/thermal conductivity on the surface of the substrate to form a synergistic effect of fluid guiding flow paths, which can further improve the conductivity and thermal conductivity of the separator.
  • a conductive/thermally conductive fluid guide flow path between adjacent separators and between the separator and the gas diffusion layer, it is possible to provide a conductive path and a heat dissipation path connecting one substrate to another substrate .
  • forming a fluid guide flow path by using a separator or a gas diffusion layer as a component of a fuel cell as a base substrate contributes to making the cell thickness thin.
  • a cooling medium flow path (including flow path ribs and a reinforcing layer) is formed between adjacent separators, and a reactive gas flow path is formed on the outside of the separator, which can also achieve a thinner base material reinforcement.
  • the role of the frame structure can improve the rigidity and strengthening of the partition.
  • FIG. 1 is a schematic diagram showing the structure of a single unit of a fuel cell in an embodiment of the present invention.
  • FIG. 2A-2C are an example of a fuel cell separator in an embodiment of the present invention
  • FIG. 2A is a plan view of the cooling medium flow path side of the separator
  • FIG. 2B is along the S of the separator corresponding to the active region.
  • the cross-sectional view of the line -S', and FIG. 2C is a cross-sectional view of the separator substrate.
  • FIG 3 is an example of a partial cross-sectional view of a separator for a fuel cell according to Embodiment 1 of the present invention.
  • FIG 4 is an example of a partial cross-sectional view of a separator for a fuel cell according to Embodiment 2 of the present invention.
  • FIG. 5 is a partial cross-sectional view of a separator for a fuel cell according to Embodiment 3 of the present invention.
  • Fig. 6 is a diagram showing an example of a planar pattern of a fluid guiding flow path attached to a separator for a polymer electrolyte fuel cell in an embodiment of the present invention.
  • Fig. 7 is an exemplary flowchart for explaining a method of manufacturing a separator in an embodiment of the present invention.
  • Embodiments 1 to 3 can be appropriately modified as long as they do not depart from the gist of the present invention. , The present invention is not limited by the embodiment at all.
  • FIG. 1 is a schematic diagram showing the structure of a single unit of a polymer electrolyte fuel cell according to Embodiments 1 to 3 of the present invention.
  • the polymer electrolyte fuel cell includes a plurality of membrane electrode assemblies MEA (Membrane Electrode Assembly).
  • a membrane electrode assembly MEA includes a polymer electrolyte membrane 1, two catalyst layers 2, 3, and two gas diffusion layers 4, 5, which constitute an anode and a cathode, respectively.
  • the two sides of the polymer electrolyte membrane 1 are coated with a catalyst coating membrane in a CCM (Catalyst Coated Membrane) manner.
  • the first side and the second side of the catalyst coating membrane correspond to the catalyst layer 2 and the catalyst layer, respectively. 3.
  • An anode electrode is arranged on one side surface of the membrane electrode assembly MEA to constitute the anode of the battery, and the cathode electrode is arranged on the other side surface to constitute the cathode of the battery.
  • the membrane electrode assembly MEA is sandwiched between the two sets of separators 6 and 7.
  • the partitions 6, 7 function as partitions separating individual units.
  • the fuel cell according to one embodiment of the present invention is a so-called single-cell structure polymer electrolyte fuel cell in which a membrane electrode assembly MEA is sandwiched between a set of separators 6 and 7.
  • a set of separators 6 and 7 includes an anode-side separator 6 and a cathode-side separator 7.
  • the catalyst layer 2 is the anode side catalyst layer 2
  • the catalyst layer 3 is the cathode side catalyst layer 3
  • the gas diffusion layer 4 is the anode side gas diffusion layer 4
  • the gas diffusion layer 5 is the cathode side gas diffusion layer 5.
  • the embodiment of the present invention adopts a stack structure in which a plurality of battery cells are stacked in series via separators 6 and 7.
  • the fuel cell stack is constructed by stacking a plurality of battery cells to form a laminate, and the current collector plates, insulating plates, and end plates are arranged in this order at both ends of the laminate.
  • reaction gas flow path 22 is formed along the surface where the reaction proceeds (referred to as the reaction surface), and the separator 6 and the separator 7 that separate adjacent individual cells are formed.
  • a cooling medium flow path 21 is formed therebetween.
  • sealing members for the purpose of airtightness and watertightness are provided on the outer edges of the above-mentioned partitions 6, 7 to prevent leakage of cooling medium, reaction gas, and the like.
  • the reaction gas flow path 22 and the cooling medium flow path 21 are collectively referred to as a fluid guide flow path. Specifically, respective reaction gas flow paths 22 are formed between the separators 6 and 7 and the gas diffusion layers 4 and 5. A cooling medium flow path 21 is formed between the partition plates 6 and 7 separating adjacent individual units. Use antifreeze agents such as water and glycol, air, etc. as the cooling medium.
  • the fuel gas anode gas
  • the fuel gas may be, for example, hydrogen gas, methane gas, or the like.
  • An oxidizing gas (cathode gas) is supplied from the reaction gas flow path 22 of the cathode side separator 7.
  • the oxidizing gas may be, for example, a gas containing oxygen such as oxygen and air.
  • the circulation system of the cooling medium in the fuel cell will be described.
  • the cooling medium cooled by the radiator is supplied to the fuel cell stack via a water pump and piping.
  • the cooling medium supplied to the fuel cell stack is distributed to the individual units via the cooling medium supply manifold, and the individual units are cooled.
  • the cooling medium after cooling each individual unit is collected through the cooling medium discharge manifold, and circulates in the radiator through the pipe.
  • the fuel gas circulation system will be described.
  • the fuel gas is supplied to the fuel cell stack from a hydrogen tank storing high-pressure hydrogen gas via a shut-off valve, regulator, and piping.
  • the fuel gas supplied to the fuel cell stack is distributed to each individual unit via a fuel gas supply manifold, and is used for power generation of each individual unit.
  • the unused fuel gas in each individual unit is collected through a fuel gas discharge manifold, and is discharged to the outside of the fuel cell stack through a discharge pipe.
  • the circulation system of the oxidizing gas will be described.
  • the oxidizing gas is supplied to the fuel cell stack via an air pump and piping.
  • the oxidizing gas supplied to the fuel cell stack is distributed to the individual units via the oxidizing gas supply manifold, and used for power generation of the individual units.
  • the unused oxidizing gas in each individual unit is collected through the oxidizing gas discharge manifold, and is discharged to the outside of the fuel cell stack through the discharge pipe.
  • fuel gas and oxidizing gas are also referred to as reaction gas.
  • the separators 6 and 7 of the present invention are roughly as shown in FIG. 2A and are composed of a rectangular flexible film material.
  • One edge in the longitudinal direction is formed with a fluid supply port 31 that is substantially rectangular in the width direction.
  • a fluid discharge port 32 that is substantially rectangular in the width direction is formed, and a fluid guide flow path is formed from the plurality of ribs 11 from the supply port 31 to the discharge port 32 (that is, along the longitudinal direction).
  • the fluid supplied from the supply port 31 flows along the fluid guide flow path, and the fluid not used for power generation is discharged through the discharge port 32.
  • the fluids here are oxidizing gas, fuel gas, and cooling medium.
  • the present invention focuses on a structure in which a fluid such as a cooling medium or a reaction gas is supplied to the active area (power generation area) of the central part of the separator substrate of the MEA.
  • a fluid such as a cooling medium or a reaction gas
  • FIG. 2A the partition on the side of the cooling medium flow path 21 is shown, and the area enclosed by the broken line corresponds to the active area.
  • the opening hole 33 of the internal manifold is formed on the outer edge of the active area of the separator of the present invention.
  • a required sealing material 20 is provided on the outer periphery.
  • Fig. 2B is a cross-sectional view taken along the line S-S' of the separator of Fig. 2A.
  • the separators 6 and 7 of the present invention are manufactured using two separator base materials 100 composed of a highly conductive/thermally conductive flexible film material.
  • the separator substrate 100 is attached by using a dedicated device (for example, coating, printing, dispensing, spraying, transfer, etc.), including conductive materials, bonding resins, solvents, other additives, and conductivity enhancement
  • a dedicated device for example, coating, printing, dispensing, spraying, transfer, etc.
  • the precursor of the material and other adhesion materials (the state before adhesion and the state before the curing reaction) forms a fluid guiding flow path on the surface of the separator substrate 100.
  • the separator of the present invention is a component of a polymer fuel cell composed of two separator base materials 100 and a cooling medium flow path 21 formed between the two separator base materials 100.
  • the anode and cathode reaction gas flow paths 22 are formed on the outer surface of the separator as described above (the surface opposite to the surface where the cooling medium flow path 21 is provided), thereby forming the anode side separator 6 and the cathode side separator. 7.
  • FIG. 2B The basic structure of the separator of the present invention will be described with reference to FIG. 2B. As shown in FIG. 2B, the main components of the separator of the present invention are shared in all the embodiments 1 to 3 described later.
  • Reactive gas flow path 22 fuel gas, oxidizing gas
  • a good separator In general, a good separator must have airtightness, so as to prevent the diffusion and mixing of various fluids in the battery, and must have sufficient conductivity in order to have a good current collector. If the separator is thick, the internal resistance will increase, so the separator cannot be too thick. For example, the thickness of the separator may be 10 to 1,000 ⁇ m. In order to release the reaction heat to the outside, the separator also needs to have thermal conductivity/dissipation properties. In addition, the separator also needs to have corrosion resistance, rigidity, and a low-cost roll-to-roll method (after attaching the flow path pattern to the substrate rolled into a cylindrical shape, it is rolled into a cylindrical shape again to make it Mass production method that continuously flows between devices) production.
  • the separator of the present invention is constructed based on the above-mentioned idea.
  • adhesion means that an adhesion material (paste, slurry, ink) having a viscosity is covered on the surface as a three-dimensional structure.
  • Coating is to cover the surface with a thinner film.
  • the substrate in the present invention refers to a member that becomes the base to which the fluid guide flow path is attached.
  • the substrate is equivalent to the separator substrate 100 forming the separators 6, 7 and the gas diffusion layer 4, 5 as the gas diffusion layer. Layer substrate.
  • the present invention will be described mainly focusing on the separator substrate 100 to which the rib structure is attached.
  • the gas diffusion layers 4 and 5 are used as the surfaces of the adhesion rib structure, the surfaces of the gas diffusion layers 4 and 5 become the adhesion surfaces.
  • the main function of the separator substrate 100 shown in FIG. 2C is to make the separator have electrical conductivity and thermal conductivity, which can cope with the mass production of the roll-to-roll method and make the total cost of the flexible structure (flexible film) low. Material), and a substrate for forming a fluid guiding flow path on its surface.
  • a sheet-like structure capable of achieving high electrical conductivity, high thermal conductivity, high output volume density, and high output weight density is used as the separator substrate 100. It is desirable that the separator substrate 100 has electrical conductivity and thermal conductivity, can be produced at a lower material cost, can be applied to a roll-to-roll method, and can achieve thinner thickness and lighter weight.
  • the separator substrate 100 includes at least one conductive material and at least one resin composition.
  • the conductive material may be a conductive carbon material.
  • the separator substrate 100 further includes at least one conductive reinforcing material.
  • the conductive reinforcing material may be a conductive carbon reinforcing material.
  • the separator substrate 100 is a highly conductive carbon composite flexible film material composed of a conductive carbon material, a resin composition, and a conductive carbon reinforcement material.
  • a conductive carbon material graphite powder, carbon powder, carbon black, etc. are mixed.
  • a resin composition a thermoplastic resin (polyethylene, polypropylene, etc.) and a thermosetting resin (phenol resin, epoxy resin, etc.) are mixed.
  • a conductive carbon reinforcement material carbon fiber, carbon nanotube, graphene, etc. are mixed. These materials are formed into a one-piece, thin and flexible high-conductivity carbon composite flexible membrane material.
  • the highly conductive carbon composite flexible film material is a material obtained by combining conductive materials, resins, and reinforcing materials.
  • the general manufacturing process of the separator substrate 100 is to laminate the above-mentioned materials, cover the laminate with an elastic film, and harden it by applying pressure/heating.
  • the characteristic of the separator substrate 100 is a sheet-like shape with a flat main surface.
  • conductive reinforcement such as reinforced resin, fine graphite fibers and/or carbon nanotubes and/or graphene is added during the molding of the separator substrate 100 material.
  • conductive reinforcing materials such as fine graphite fibers and/or carbon nanotubes are arranged on the extended surface of the separator substrate 100 in a vertical direction or Aligned in an oblique through direction.
  • the separator substrate 100 that can be used in the present invention, as long as it has a thin thickness and a light weight, it can provide water tightness and/or air tightness in which the cooling medium and reaction gas are not mixed, and the conductivity and thermal conductivity are relatively high.
  • the material is high and can withstand chemical changes such as degradation. It is a flexible film with a thickness suitable for roll-to-roll mass production. It is not limited to the above-mentioned high-conductivity carbon composite flexible film, and ready-made products can also be widely used. Know items.
  • the thickness of the separator base 100 is preferably in the range of 10 to 100 ⁇ m, and more preferably in the range of 10 to 50 ⁇ m.
  • the electrical conductivity of the separator is improved by the electrical conductivity of the separator base 100 and the electrical conductivity of the functional material constituting the fluid guiding flow path.
  • the carbon fiber contained in the separator substrate 100 and the functional material of the fluid guiding flow path is a material with good electrical or thermal conductivity.
  • a flexible film material can be produced by orienting graphite, which is a material with good thermal conductivity, which has a heat dissipation function to efficiently release heat generated by power generation, and is difficult to Deterioration is caused, and thermal conductivity can be additionally increased.
  • the thermal conductivity of the separator substrate 100 is at least about 700 W/mk.
  • the surface treatment layer and/or the surface modification layer 105 coat the separator substrate 100 to reduce the surface contact resistance of the substrate and improve the adhesion and adhesion between the substrate and the reinforcing layer 106 or the fluid guiding flow path described later. ⁇ The layer.
  • the surface treatment layer and/or the surface modification layer 105 are not provided on the gas diffusion layer base material. In order to reduce the contact resistance value and improve the adhesion and adhesion with the separator substrate, it is necessary to apply a special surface treatment to improve compatibility. If the interface adhesion and adhesion are insufficient, the electrical conductivity will gradually be lost over a long period of time, the electrical resistance will increase, and the power generation performance will deteriorate.
  • surface pretreatment is performed to improve the wettability of the substrate surface.
  • various coating methods such as spin coating, slit coating, spray coating, dip coating, bar coating, etc., sputtering in various gases, chemical vapor deposition, and physical vapor deposition can be included. Vapor deposition method, and other appropriate methods, etc.
  • etching with chemicals such as acid, plasma treatment, corona discharge treatment, frame treatment, ozone treatment, ultraviolet treatment, and other appropriate treatments can be included.
  • FIG. 2C A typical example of the separator substrate 100 formed with the surface treatment layer and/or the surface modification layer 105 is shown in FIG. 2C.
  • the method of immersing the separator substrate 100 in the treatment liquid for surface modification is adopted, and the treatment liquid used should preferably be a treatment liquid that does not invade the substrate.
  • the surface treatment layer and/or the surface modification layer 105 can be obtained.
  • the thickness of the surface treatment layer 105 may be 1 to 1,000 nm.
  • the thickness of the surface modification layer 105 may be 0.1 to 1,000 nm.
  • the surface treatment layer and/or the surface modification layer 105 at least on the separator substrate 100 adhered to the fluid guide flow path described later. Single side.
  • the separator for the polymer electrolyte fuel cell has a flow path of the reaction gas containing water vapor, and is used under high temperature and acidic conditions to maintain the corrosion resistance of the surface treatment layer and/or the surface modification layer 105. very important.
  • the surface treatment layer and/or the surface modification layer 105 serves as a conductive layer with conductivity, and it is also important to cover both sides of the separator substrate 100.
  • the reinforcement layer 106 is a layer that can be coated on the surface treatment layer and/or the surface modification layer 105 to which the separator substrate 100 is subjected to surface treatment and/or surface modification treatment.
  • the reinforcing layer 106 is not provided on the gas diffusion layer base material. Since the separator substrate 100 is a very thin material, it is desirable to strengthen the separator substrate 100. Therefore, as shown in FIG. 2C, it is recommended to provide a strengthening layer 106 on the above-mentioned surface treatment layer and/or surface modification layer 105.
  • the thickness of the reinforcement layer 106 may be 1-50 ⁇ m.
  • a reinforcing layer 106 may be provided on the side facing the cooling medium flow path 21.
  • a hydrophobic coating is applied to the reinforcement layer 106, and the contact angle indicating the wettability is set to a medium level, so that the three-dimensional shape of the rib 11 structure can be processed. modeling.
  • the material of the reinforcement layer 106 may be the same material as the adhesion material of the cooling medium flow path 21 and the adhesion material of the reaction gas flow path 22 described later, may be different from their mixing ratio, or may be a heterogeneous material. s material.
  • the reinforcement layer 106 may be provided on the entire surface of the active area of the separator substrate 100 after the surface treatment/surface modification has been completed, the reinforcement layer 106 may be provided locally, or the reinforcement layer 106 may not be provided.
  • the material of the strengthening layer 106 as long as it has conductivity and thermal conductivity, can be coated on the surface treatment layer and/or the surface modification layer 105, the surface treatment layer and/or the surface modification layer 105 and various fluids guide flow
  • the adhesive material of the road has good adhesion and adhesiveness, and can contribute to the improvement of the rigidity of the separator substrate 100, and it is not particularly limited.
  • the cooling medium flow path 21 is a flow path located between the two separator substrates 100 (the first separator substrate 101 and the second separator substrate 102).
  • a cooling medium flow path 21 is formed on the surface of at least one of the two separator substrates 100.
  • the cooling medium flow path 21 is formed in the first separator substrate 101, and the second separator substrate 102 and the first separator substrate 102 are bonded together.
  • the cooling medium flow path 21 is not provided in the bonded second separator substrate 102. By bonding the two separator base materials together, the cooling medium flow path 21 is completed in the middle of the two separator substrates.
  • the ribs 11 of the cooling medium flow path 21 may be alternately provided on the first separator substrate 101 and the second separator substrate 102 and meshed.
  • the height of the fluid guide flow path including the cooling medium flow path 21 and the gas guide flow path 22 may be 1 to 500 ⁇ m.
  • the shape of the cooling medium flow path 21 is not particularly limited, and can be designed with various changes within the scope of the subject matter, such as a serpentine shape, a linear shape, a zigzag shape, a stripe shape, a pit shape, and the like.
  • the functional material (hereinafter referred to as an adhesion material) that shapes the plurality of ribs 11 (protrusions of the fluid guide flow path) constituting the cooling medium flow path 21 is not particularly limited.
  • Adhesion methods such as coating, printing, dispensing, spraying, transfer, etc. can be used, and the precursor of the adhering material (paste, slurry, or ink) can be adhered, heated/dried, as long as the result can be obtained What is necessary is just an adhesion material which functions on the board base material 100.
  • the material before heating/drying of paste, slurry, ink, etc. is referred to as "precursor of adhesion material"
  • the heated/dried material covering the separator substrate 100 is referred to as It is the "attachment material”.
  • attachment materials there are dense carbon-based materials and/or porous carbon-based materials.
  • the rib 11 constituting the cooling medium flow path 21 is a highly conductive adhesive material.
  • the adhesive material needs to have a level of heat resistance that does not deform at the operating temperature of the fuel cell or at the pressure bonding temperature such as hot stamping.
  • the rib 11 With higher conductivity, high mechanical strength, and high heat resistance strength can be obtained. Therefore, as the adhesion material, there is no limitation as long as it has excellent electrical conductivity and good thermal conductivity, is hard to be deteriorated, and can impart rigidity/reinforcement.
  • the separator as described above is provided with a cooling medium flow path 21 on at least one surface of a single separator substrate 100.
  • the channel as the reaction gas flow path 22 (that is, the fuel gas flow path and the oxidizing gas flow path) is formed on the outer surface of the separator. road).
  • the reaction gas flow path 22 may be provided on one side of the two bonded separator substrates 100, or part or all of the reaction gas flow path 22 may be provided on the surface of the gas diffusion layer substrate.
  • the efficiency of the fuel cell itself can also be improved.
  • the height of the ribs of the fluid guide flow path attached to the thinner substrate surface is determined by the pressure loss requirements of the reactant gas, etc., so the thickness of the cell separator can be made thinner.
  • the cell pitch becomes narrower.
  • the output volume density of the fuel cell can be improved.
  • the height of the fluid guiding flow path may be 1 to 500 ⁇ m.
  • a reaction gas flow path 22 through which fuel gas passes is formed on a separator surface opposite to the anode gas diffusion layer 4 of the membrane electrode assembly MEA.
  • the other flat surface is in contact with the cooling medium flow path 21.
  • a reaction gas flow path 22 through which oxygen-containing oxidizing gas passes is formed on one of the separator surfaces facing the cathode side gas diffusion layer 5 of the membrane electrode assembly MEA.
  • the other flat surface is in contact with the cooling medium flow path 21.
  • Each reactive gas flow path may be provided on any outside of the bonded separator substrate 100. In this way, the supply of reactant gas is received, and the fuel cell of the present invention generates power.
  • the separator in which the cooling medium flow path 21 is provided between the two separator substrates 100 and bonded together can be said to be a common member for the anode and cathode of the fuel cell.
  • the anode side and the cathode side are recognized.
  • each reaction gas flow path 22 is not particularly limited, and various changes can be made within the scope of its theme to design separately, such as a serpentine shape, a serpentine rotation shape, a linear shape, a pit shape, or other shapes. Wait.
  • the adhesion material that shapes the plurality of ribs 12 (protrusions of the fluid guide flow path) constituting the reaction gas flow path 22 is not particularly limited.
  • adhesion methods such as coating, printing, dispensing, jetting, and transfer can be used, and the precursor (paste, slurry, or ink) of the adhesion material can be adhered and heated/ Drying, as long as the result is that an adhesive material having a function of covering the separator substrate 100 can be obtained.
  • attachment materials there are dense carbon-based materials and/or porous carbon-based materials. The attachment material is attached to the surface of the separator and/or the surface of the gas diffusion layer facing the separator.
  • the rib 12 of the reaction gas flow path 22 is a highly conductive adhesive material. Therefore, as the adhesion material of the reaction gas flow path 22, it is desirable to be a material that has excellent electrical conductivity and good thermal conductivity, is hard to be deteriorated, and can impart rigidity and strengthening properties.
  • the same material as the adhesion material used for the cooling medium flow path 21 can be used as the adhesion material that can be used for each reaction gas flow path 22.
  • the composition of the adhesion material can be partially different according to the characteristics required for each fluid guide flow path.
  • Each reaction gas flow path may use the same adhesion material for the anode and the cathode, or a heterogeneous adhesion material.
  • a porous carbon-based material is used as the adhesion material of the reaction gas flow path 22 since there are voids, heat can be efficiently taken away from the cooling target. This is because the existence of voids can ensure air permeability, so when the abundant liquid such as water existing on the cathode side vaporizes, the heat of vaporization is taken away from the surroundings and has a cooling effect.
  • a porous carbon-based material is preferably used as an attachment material for an oxidizing gas flow path.
  • the term "adhesion/adhesion” mentioned in the present invention means between the surface of the separator substrate 100 and the surface treatment layer and/or the surface modification layer 105, between the surface treatment layer and/or Between the surface modification layer 105 and the reinforcing layer 106, between the surface treatment layer covering the separator substrate 100 and/or between the surface modification layer 105 and the bottom of the rib 11 of the cooling medium flow path, and between the covering separator substrate 100 100 between the surface treatment layer and/or surface modification layer 105 and the bottom of the rib 12 of the reaction gas flow path, between the reinforcing layer 106 and the bottom of the rib 11 of the cooling medium flow path, between the reinforcing layer 106 and the bottom of the rib 11
  • the materials constituting (1) to (5) are not particularly limited, and the functions required for each component are grasped, the most suitable materials are selected according to the requirements, and the characteristics of these constituent materials are appropriately used.
  • the manufacturing method of the separator of the present invention is not particularly limited, as long as the desired structure and material of the separator substrate 100, the material of the fluid guiding flow path, the product shape of other fuel cell components, etc. are taken into consideration, an appropriate selection is made. The preferred conditions are sufficient.
  • Embodiment 2 based on the basic manufacturing method described in Embodiment 1, the description focuses on different structures and processes.
  • the description is focused on different structures and processes.
  • Embodiment 1 of the present invention the basic flow of the separator and its manufacturing method in Embodiment 1 of the present invention will be described.
  • the structure and manufacturing method of the separator according to Embodiment 1 described below are a reference, and the present invention is not limited to this.
  • manufacturing processes and steps can be appropriately added, omitted, or changed in accordance with the structure or shape of the component parts, the materials used, and the combination of materials or types.
  • the cooling medium flow path 21 is attached between two conductive separator base materials 100 to form a separator main body.
  • the separator substrate 100 functions as a bottom plate on which the rib 11 of the cooling medium flow path is formed.
  • the rib 11 constituting the channel through which the cooling medium passes is attached to the separator substrate 100, so it is not necessary to mold the separator substrate 100 into a groove-shaped flow path shape as in the past. That is, after cutting the separator base material 100 to the size required for the separator, the ribs 11 constituting the cooling medium flow path may be attached.
  • the reaction gas flow path is attached to each gas diffusion layer 4, 5 side instead of the separator 6, 7 side. Therefore, in the above case, it is not on the separator side. Set up the reaction gas flow path.
  • the separator requires moderate rigidity and conductivity.
  • the thickness of the fuel cell separator of the present invention may be 10 to 1,000 ⁇ m.
  • a conductive flexible film material having a thin thickness is used as the separator substrate 100 for description.
  • a conductive flexible film material (10 m ⁇ cm 2 or less) having a low electrical resistance is used as the separator substrate 100 to form the separator of the present invention.
  • the thickness of the separator substrate 100 may be 10-50 ⁇ m.
  • a separator located in the range of the active area in the center is used as the separator of Embodiment 1.
  • the separator substrate 100 used in the separator is cut into a desired size by cutting a conductive flexible film material Obtained.
  • a precursor (paste, slurry, or ink) of the attachment material that becomes the raw material is selectively attached to the separator substrate 100 and heated/ dry.
  • the components contained therein are typically a conductive material, a binder resin, a dispersion solvent, and a carbon-containing conductive paste of various additives.
  • Each component can be used singly, or two or more can be mixed to improve physical properties or reduce price.
  • a mixer/defoaming device can be used as an example of a device that uniformly mixes the above-mentioned ingredients.
  • Paste attachment liquid precursor of attachment material
  • the adhesion method of the fluid guide flow path may be a known method, for example, an adhesion method using an apparatus capable of spreading adhesion methods such as coating, printing, dispensing, spraying, and transfer. Since the ribs 11 and 12 of the flow path are formed by repeated fixation of a small amount of adhesion, it is desirable to use an automatic control device for adhesion. It is possible to use attachment devices (flow path forming devices) including screen printers, inkjet printers, spraying machines, roller coaters, dispensers, 3D printers, and other suitable devices to selectively cover only the fluid guiding flow paths The ribs 11,12. In other words, these devices are used to perform partial attachment, thereby shaping the ribs 11 and 12 on the surface of the base material. In addition, in order to correct the deformation of the substrate and perform attachment, a roll-to-roll attachment device can be introduced. These automatic control attachment devices help improve productivity.
  • surface treatment may be performed after the adhesion process.
  • the attached ribs 11, 12 may be treated with carbon coating, water repellency, or hydrophilic treatment. These treatments can increase the surface treatment layer and/or the surface treatment layer applied to the surface of the separator substrate 100.
  • the interface adhesion and adhesion between the surface modified layer 105 (or the reinforced layer 106) and the ribs 11 and 12 of the flow channel can also improve the drainage of the reaction water.
  • the height of the fluid guide channel may be, for example, 1 to 500 ⁇ m. Since the fuel gas flow path and the oxidizing gas flow path are attached to the surface of one side of the gas diffusion layers 4 and 5, the separator body that adheres the two separator substrates 100 together is the unspecified anode side separator 6, cathode
  • the side partition 7 (the reaction gas flow path is not formed on the side of the partition) is a common partition. Therefore, the degree of freedom in the process management of the partition member is increased, and the assembly can be rationalized.
  • FIG. 7 is an exemplary flowchart for explaining the method of manufacturing the separator in Embodiments 1 to 3.
  • the manufacturing method of the separator is performed by the following steps [1] to [8].
  • Step [1] forming a substrate, this step is referred to as a substrate manufacturing step;
  • Step [2] cut the substrate to the required size, and call this step the cutting step;
  • Step [3] forming a modified treatment layer on the surface of the substrate, this step is referred to as a surface treatment step;
  • Step [4] forming a strengthening layer, this step is called a strengthening layer forming step;
  • Step [5] forming a cooling medium flow path, this step is referred to as a cooling medium flow path forming step;
  • Step [6] laminating the substrate, this step is called the laminating step
  • step [8] a reaction gas flow path is formed, and this step is referred to as a reaction gas flow path forming step.
  • the basic manufacturing method of the separator of the present invention includes a base material production step [1], a cutting step [2], a surface treatment step [3], a strengthening layer forming step [4], a cooling medium flow path forming step [5], A total of 8 steps are the bonding step [6], the pressurizing and heating treatment step [7], and the reaction gas flow path forming step [8].
  • a total of 7 steps including steps [1], [2], [3], [5], [6], [7], and [8] are implemented.
  • a strengthening layer forming step [4] of forming the strengthening layer 106 is added.
  • a part of the strengthening layer forming step [4] is skipped, and a step of simultaneously attaching the strengthening layer 106 and the ribs 12 is added to the forming step [8] of the reaction gas flow path 22.
  • the substrate preparation step [1] the conductive material, the resin composition, and the reinforcing material are combined and wound (mixed, laminated, coated, pressurized/heated, and completed) to form the separator substrate 100.
  • the cutting process [2] proceed to the cutting process [2].
  • the separator substrate 100 (for example, a thickness of about 50 ⁇ m, a conductivity of 500 S/cm, and a thermal conductivity of 1700 W/mk) is cut to a desired size.
  • a cutting process of cutting the separator substrate 100 into a rough shape is performed.
  • the separator substrate 100 is a very thin material, the work of cutting to a desired size will be easier.
  • the surface of the separator substrate 100 is cleaned in advance, and a step of forming a surface treatment layer and/or a surface modification layer 105 on the surface is performed.
  • a cleaning process to remove foreign matter or contamination on the surface of the substrate, and then use the same material as the adhesion material to form a coating (surface treatment layer), etc.
  • the surface treatment layer 105 having an inclined functional structure in which the total content rate of the carbon component in the surface treatment layer 105 increases from the substrate side to the other material layer (such as the reinforcement layer 106 etc.) side, or it can be implemented as a countermeasure
  • the covering surface of the separator substrate 100 is subjected to surface modification treatments such as corona treatment, low-temperature plasma treatment, chemical treatment, solvent treatment, and other appropriate treatments such as pretreatment for modification.
  • the thickness of the surface treatment layer 105 may be 1 to 1,000 nm.
  • the thickness of the surface modification layer 105 may be
  • the cooling medium flow path forming step [5] only one separator substrate 100 (for example, the first separator substrate 101) of the two separator substrates 100 that has been surface-modified in advance is formed
  • the ribs 11 of the cooling medium flow path may be alternately provided on the two separator substrates 100 (the first separator substrate 101 and the second separator substrate 102).
  • the process of providing the reinforcement layer 106 may be performed before the formation of the fluid guide flow path, but the process is arbitrary. In the first embodiment, as shown in FIG. 3, it is shown that the process is not provided.
  • the reinforcing layer 106 is an example in which the rib 11 is directly attached to the surface-treated separator substrate 100, and the effect of reducing the thickness of the separator can be obtained.
  • various flow path patterns as shown in FIG. 6 can be flexibly used, and the overall frame structure of the thin separator substrate 100 can be used to provide the fluid guiding flow path, which can strengthen the separator. effect.
  • flow path forming devices that can adopt coating, printing, dispensing, jetting, transfer, etc. methods include screen printers, inkjet printers, dispensers, and sprayers. , Roller coater, and other reasonable devices, etc. attachment devices.
  • the drying temperature after adhesion is related to the drying speed and can be selected according to the nature of the material used. In the process of forming the fluid guiding flow path on the surface of the substrate, the shorter the drying time, the better. In the drying process, the unnecessary solvent is volatilized and removed. Next, proceed to the bonding step [6].
  • the pasting step [6] can sandwich the sealing material 20 around the fluid guide flow path on one substrate on which the fluid guide flow path is formed, and bond the other substrates. It is important to perform bonding while adjusting, so as to squeeze out the air at the interface between the base material and the ribs 11 and 12, and to prevent the adhesion material from intruding into the space of the channel portion of the flow path.
  • the ribs 11 of the cooling medium flow path are alternately provided on the two separator substrates 100, it is also possible to manually attach the ribs 11 so that the ribs 11 mesh with each other, or the next process can be considered. , Use automatic laminating devices that can continuously and automatically laminate, etc. Next, proceed to the pressure heating treatment step [7].
  • the bonded separator substrate 100 is pressure-bonded with a press machine.
  • the crimping method may be, for example, pressing by a roller, pressing with a load, pressing with a clamp or a torque wrench, cold pressing of a turnbuckle, hot pressing, and other methods. It can also be performed in one of radiation, conduction, and convection as a general heating method. Heating by conduction is a contact method, and heating by radiation and convection is a non-contact method.
  • each of the ribs 11 can be heated by applying a surface pressure (pressing force of 0.01-10 MPa) in a conductive contact manner using a hot press from two surfaces.
  • the pressure and heating treatment that can apply a predetermined surface pressure and harden it, the bonding component contained in the bonding resin near the interface of the rib 11 or the reinforcing layer 106 can be used to bond the interface and completely remove it. The remaining moisture or dispersant and other ingredients. In addition, residual stress can be removed.
  • the basic shape of the separator of Embodiment 1 of the present invention is completed.
  • the fuel gas flow path ribs 12 are attached to the gas diffusion layer of the first embodiment. 4 to form the anode side separator 6 on one side.
  • the cathode side separator 7 is formed by attaching the oxidizing gas flow path rib 12 to one surface of the gas diffusion layer 5 of the first embodiment.
  • the substrate to which at least one of the fuel gas flow path and the oxidizing gas flow path is attached it is not necessary to use the separator substrate 100 but the gas diffusion layer substrate.
  • the reactive gas flow path ribs 12 are attached to the surfaces of the gas diffusion layers 4 and 5, the reactive gas flow path 22 is not attached to the outer surface of the separator main body sandwiching the cooling medium flow path 21.
  • the ribs 12 of the reaction gas flow path are attached to the surfaces of the gas diffusion layers 4 and 5 on the opposite side of the separator.
  • the ribs 12 are directly attached to the gas diffusion layers 4 and 5 s surface.
  • the surface of the gas diffusion layers 4 and 5 to which the reaction gas flow path 22 is attached is brought into contact with the corresponding separator surface, thereby forming the channel portion of the reaction gas flow path 22.
  • the substrate surface of the rib 12 to which the reaction gas flow path is attached is not particularly limited, and may be the gas diffusion layers 4 and 5 or the separators 6 and 7.
  • the adhesion material of the rib 12 constituting the reaction gas flow path attached to the surface of the gas diffusion layer base material and the adhesion material of the rib 11 constituting the cooling medium flow path may be the same, as long as they are conductive and thermally conductive materials. , Can be different locally or different on the entire surface.
  • the structure, material composition, and mixing ratio similar to those of the reaction gas flow path 22 attached to the anode side gas diffusion layer 4 and the cathode side gas diffusion layer 5 can be applied, and different structures and materials can also be applied. Composition and mixing ratio.
  • FIG. 3 shows an example of a separator in which a fuel gas flow path and an oxidizing gas flow path are formed on the gas diffusion layer side.
  • the attachment device that forms these reaction gas flow paths 22 for example, flow path forming devices such as coating, printing, dispensing, spraying, and transfer methods, micro-ejection devices, and other suitable devices are used.
  • the heating process when forming the reaction gas flow path 22 is not particularly limited, but it is desirable to use an electric heater in a non-contact method of radiation to emit infrared rays to heat from the inside.
  • resins are suitable for infrared heating with a wavelength of 3 to 3.5 microns.
  • infrared rays penetrate into the separator substrate 100, the ribs 11, 12, or the reinforcing layer 106, there is an advantage that it can be heated to a deeper portion.
  • the bonding component of the bonding resin contained in the vicinity of the interface of the ribs 11 and 12 or the reinforcement layer 106 brings the interface into close contact, and the remaining moisture, dispersant, and other components are volatilized. In addition, residual stress can be removed.
  • the reaction gas flow path 22 there are two types of the fluid guide flow path according to the present invention, the reaction gas flow path 22 and the cooling medium flow path 21.
  • the reaction gas flow path 22 there are two types of fuel gas flow paths (anode) and oxidizing gas flow paths (cathode).
  • the fluid guide flow path of the present invention is different from the integrated gas flow path of the substrate and the flow path commonly used in the generally used separator or gas diffusion layer, in that the ribs 11 and 12 constituting the fluid guide flow path are formed in the gas diffusion layer 4, 5 and partitions 6, 7 between such specifications.
  • the fluid guiding flow path to which the present invention is applied is not integrated with the separators 6, 7 or the gas diffusion layers 4, 5, but is located independently in the middle of these substrates, and the flow path ribs 11, 12 are
  • the base material of the base material is different. That is, it can be understood that the flow path ribs 11 and 12 and the reinforcement layer 106 belong to the fluid guiding flow path, and the surface treatment layer and/or the surface modification layer 105 belong to the separator base material.
  • the reaction gas flow path 22 will be described in detail using Embodiments 2 and 3.
  • both of them are the same type of conductive flexible film material, but it is not necessary to be the same type of conductive flexible film material. If the contact resistance is low, Different types of conductive flexible film materials that are flat and thin are possible.
  • the present invention has the feature of providing the cooling medium flow path 21 between the two separator substrates 100 of more than one conductive flexible film material, and is a flexible separator that can adopt a roll-to-roll method (flexible separator: Flexible partition).
  • the separator according to the first embodiment also has the following function: acting as a flow path through which the cooling medium flows through the cooling medium flow path 21 provided between the two separator base materials 100,
  • the partitions 6, 7 between the units perform the function of combining, provide conductive paths and heat dissipation paths, and strengthen the rigidity of the partition body.
  • a thin conductive flexible film with excellent electrical conductivity, thermal conductivity, and gas impermeability is used as a separator substrate, and a gas impermeable sealing material 20 that can achieve no mixing of reactive gases is used.
  • the ribs 12 of the reaction gas flow path are formed on the surface of the gas diffusion layer substrate (the surface of the gas diffusion layer facing the separator side), thereby realizing a separator having electrical conductivity, thermal conductivity, and gas impermeability.
  • the structure and manufacturing method of the fuel cell separator according to the first embodiment of the present invention are only an example, and of course not limited to the content described in this specification.
  • separator in which the conductive flexible film material as the separator base 100 is reinforced will be described. Others are the same as the first embodiment.
  • the separator substrate 100 in the second embodiment uses both the substrate on which the rib 11 of the cooling medium flow path is formed and the substrate on which the reaction gas flow path 22 is formed.
  • the constituent material of the separator substrate 100 and the adhesion material forming the various fluid guide flow paths contain a conductive material, so that the entire separator can have conductivity and Thermal conductivity.
  • the rib 12 constituting the reaction gas flow path may be formed of the same material as the rib 11 constituting the cooling medium flow path, or may be formed of a different material.
  • the material constituting the surface treatment layer and/or the surface modification layer 105 and/or the reinforcement layer 106 may be the same as the material of the ribs 11 and 12, or may be partly different, and the mixing ratio may be adjusted according to various requirements. Adjustment.
  • the manufacturing method of the separator in Embodiment 2 of the present invention is performed through the following steps [1] to [8] shown in FIG. 7.
  • the manufacturing method of the separator of the present invention includes a base material preparation step [1], a cutting step [2], a surface treatment step [3], a strengthening layer formation step [4], and cooling
  • the medium flow path forming step [5], the bonding step [6], the pressurizing and heating treatment step [7], and the reaction gas flow path forming step [8] are 8 steps in total.
  • a total of 7 steps of steps [1], [2], [3], [5], [6], [7], and [8] are implemented.
  • the strengthening layer forming step [4] is added.
  • the characteristics of Embodiment 2 of the present invention namely, the strengthening layer forming step [4] and the reaction gas flow path forming step [8] will be described.
  • the strengthening layer forming step [4] is performed.
  • the reaction gas flow path forming step [8] is performed.
  • the side of the separator facing the cooling medium flow path 21 is first coated to increase the rigidity of a very thin separator substrate.
  • the layer 106 is subsequently attached to the ribs 11 of the cooling medium flow path.
  • the thickness of the reinforcement layer 106 may be 1-50 ⁇ m.
  • the reinforced layer 106 formed with the same or different material as the flow path attachment material has the function of making the separator substrate with a thinner thickness rigid, preventing the separator substrate from corroding, and improving the connection with the flow path ribs 11 , 12 The role of bonding and adhesion.
  • the strengthening of the separator substrate 100 can be achieved by using the flow path pattern shown in FIG. 6, for example.
  • the side of the separator substrate opposite to the gas diffusion layer is coated with a very thin layer to increase the rigidity of the separator substrate.
  • the ribs 12 of the reaction gas flow path are attached thereon.
  • the reinforcing layer 106 formed with the same or different material as the adhesion material simultaneously has the function of stiffening the separator substrate with a thin thickness, preventing corrosion of the separator substrate, and improving the connection between the ribs 11, and the flow path. 12.
  • the strengthening of the separator substrate 100 can be achieved by using the flow path pattern shown in FIG. 6, for example.
  • the coating method of the reinforcement layer 106 may be a well-known method, for example, it may include: a film forming device, a spraying machine, and a dispenser covered by a reinforcement layer forming device using coating, printing, dispensing, spraying, transfer, etc. , Coater, inkjet, spray coating, roller coating device and other suitable devices. It is desirable to automatically control the attachment device for attachment (coating, printing, dispensing, spraying, transfer). This automatic control attachment device helps to improve productivity. Of course, it is also possible to use a single multi-function attachment for the device forming the fluid guide flow path, the device forming the strengthening layer 106, and the device used when the plating film is formed as the surface treatment layer and/or the surface modification layer 105. Device to form.
  • FIG. 4 shows an example of a separator in which the ribs 12 of the fuel gas flow path and the ribs 12 of the oxidizing gas flow path are formed on the reinforcing layers 106 formed on the two separator base materials 100.
  • reaction gas flow path 22 is provided on the side of the separator substrate, as part of the reaction gas flow path formation step [8], roll coating, spray coating, printing, or brush coating can be used.
  • a hydrophilic coating liquid, a hydrophobic water-based coating, or a waterproof coating liquid will be adhered to the entire surface or part of the reaction gas flow path 22.
  • the work of attaching the hydrophilic coating liquid or the like may be performed only on the bottom of the channel portion of the reaction gas flow path 22.
  • the planar pattern of the reaction gas flow path 22 formed on the anode side separator 6 and the cathode side separator 7 can be formed into a serpentine shape, a serpentine rotation shape, a linear shape, a pit shape, and others, as long as the ribs are designed
  • the position makes the fuel cell have excellent power generation characteristics such as electrical conductivity, thermal conductivity that can efficiently dissipate power generation heat, and effectively guide fluid from the supply port of each fluid to the discharge port.
  • the surface of the base material of the rib 12 to which the reaction gas flow path is attached is not particularly limited, and may be the gas diffusion layers 4 and 5 or the separators 6 and 7. Alternatively, it may be alternately attached to the surface of the separator substrate 100 and the surface of the gas diffusion layer substrate opposed to it so that the attachment positions of the reaction gas flow path ribs 12 do not overlap.
  • the present invention is characterized in that a cooling medium flow path 21 is provided between two separator substrates 100 composed of one or more conductive flexible film materials, and the cooling medium flow path 21 is sandwiched outside the separator main body.
  • the reaction gas flow path 22 is formed on the surface, and a flexible separator (flexible separator) produced by a roll-to-roll method can be used.
  • the separator according to Embodiment 1 has a function of acting as a flow path through which the cooling medium flows through the cooling medium flow path 21 provided between two separator base materials, and acts as a flow path for the partition between two single battery cells.
  • the plates 6 and 7 perform the function of combining, provide a conductive path and a heat dissipation path, and strengthen the rigidity of the partition body.
  • the reaction gas flow path 22 on at least one side surface of the separator, the anode side separator 6 and the cathode side separator 7 can be distinguished.
  • a thin conductive flexible film with excellent electrical conductivity, thermal conductivity, and gas impermeability is used as a base material, and a gas impermeable sealing material 20 that can achieve no mixing of reactive gases is used to strengthen
  • the ribs 11 and 12 of the cooling medium flow path and the reaction gas flow path are formed on the layer 106, so that a separator with electrical conductivity, thermal conductivity, gas impermeability, rigidity, and reinforcement can be realized.
  • the separator of Embodiment 2 the structure, material composition, and mixing ratio similar to those of the anode-side separator 6 and the cathode-side separator 7 can be applied, and different structures, material compositions, and mixing ratios can also be applied.
  • the same conductive flexible film material is used as the two substrates, but the anode-side substrate and the cathode-side substrate may be different kinds of substrates.
  • Embodiment 3 a separator in which a conductive flexible film material as a separator base material is reinforced will be further described. Others are the same as the second embodiment.
  • reaction gas flow paths 22 there are two types of reaction gas flow paths 22: fuel gas flow paths and oxidizing gas flow paths.
  • the flow path shape corresponding to each reaction gas is attached to both surfaces of the separator main body in Embodiment 2, and the anode side and the cathode side of the separator can be distinguished through this process.
  • the separators described in Embodiments 1 and 2 are provided between the battery cells and the cells. Therefore, when the anode flow path is installed on one side of the separator, the other side of the separator will inevitably become the cathode.
  • the third embodiment differs from the second embodiment in that the reinforcing layer 106 is not provided on the side of the separator substrate of the reactive gas flow path 22 provided with the separator of the second embodiment, and the reactive gas is directly formed on the surface of the substrate. ⁇ 22 ⁇ Flow path 22. Except for this, the separator was produced in substantially the same manner as in the second embodiment.
  • Embodiment 3 of the present invention will be described with reference to FIG. 7.
  • the manufacturing method of the separator according to Embodiment 3 described below is a reference, and the present invention is not limited to this.
  • manufacturing processes and steps can be appropriately added, omitted, or changed in accordance with the structure or shape of the component parts, the materials used, and the combination of materials or types.
  • the manufacturing method of the separator in Embodiment 3 of the present invention is performed through the following steps [1] to [8] shown in FIG. 7.
  • the manufacturing method of the separator of the present invention includes a base material preparation step [1], a cutting step [2], a surface treatment step [3], a strengthening layer formation step [4], and cooling
  • the medium flow path forming step [5], the bonding step [6], the pressurizing and heating treatment step [7], and the reaction gas flow path forming step [8] are 8 steps in total.
  • a total of 8 steps of steps [1], [2], [3], [4], [5], [6], [7], and [8] are implemented.
  • Embodiment 3 of the present invention a part of the strengthening layer forming step [4] is skipped, and after the pressurizing and heating treatment step [7] is completed, the reaction gas flow path forming step [8] is performed.
  • the reinforcing layer 106 is provided on the side of the separator substrate to which the cooling medium flow path 21 is attached, and the reactive gas flow path 22 is attached to the partition.
  • the reinforcing layer 106 is not provided on the side of the board substrate.
  • a very thin membrane can be reasonably formed on the separator surface on the side where the reaction gas flow path is formed, which can improve the performance of the separator substrate 100.
  • the rib 12 is attached to the rigid reinforcement 106A.
  • FIG. 5 an example of the rib 12 closely adhering to the reaction gas flow path is shown using the partial enlarged view on the upper right.
  • a reinforced portion 106A is inevitably formed on the surface of the base material corresponding to the reinforced layer 106.
  • the reinforced portion 106A is formed at the same time as the rib portion 12 of the reaction gas flow path.
  • the reinforced part 106A coated in the same manner as such an adhesion material not only has electrical conductivity and thermal conductivity, but also has a function of strengthening a thin substrate on the entire surface and a function of preventing corrosion of the separator substrate 100.
  • the heating treatment performed after the reaction gas flow path 22 is shaped on the surface of the separator substrate 100 is not particularly limited, and it is desirable to use an electric heater in a radiant non-contact manner to emit infrared rays and heat from the inside.
  • an electric heater in a radiant non-contact manner to emit infrared rays and heat from the inside.
  • infrared rays penetrate into the separator substrate 100, the ribs 11, 12, or the reinforcing layer 106, there is an advantage that it can be heated to a deeper portion.
  • the bonding component of the bonding resin contained in the vicinity of the interface between the separator substrate 100, the ribs 11, 12, or the reinforcing layer 106 is used to bond the interface, and the remaining moisture, dispersant and other components are volatilized and removed. Residual Stress.
  • a flow path forming device that uses coating, printing, dispensing, spraying, transfer, etc. includes: screen printers, inkjet printers, etc. , Sprayers, roller coaters, glue dispensers, and other reasonable attachment devices.
  • the present invention is characterized in that a cooling medium flow path 21 is provided between two base materials composed of more than one conductive flexible film material, and a reactive gas flow path 22 is formed on the other side of at least one of the base materials.
  • Flexible separators flexible separators generated by roll-to-roll methods can be used.
  • the separator according to the third embodiment has a function of acting as a flow path through which the cooling medium flows through the cooling medium flow path 21 provided between the two separator base materials 100, and acts as a flow path between the two cells.
  • the partitions 6, 7 between the partitions have the function of combining, providing conductive paths and heat dissipation paths, and strengthening the rigidity of the partition main body.
  • the reaction gas flow path 22 on at least one side surface of the separator, the anode side separator 6 and the cathode side separator 7 can be distinguished.
  • a thin conductive flexible film material with excellent conductivity, thermal conductivity, and gas impermeability is used as a base material, and a gas impermeable sealing material 20 that can achieve no mixing of reactive gases is used, and a reinforcing layer 106 and the ribs 12 of the cooling medium flow path attached to the reinforcing layer 106 strengthen the separator, and at the same time, the ribs 12 and the reinforced portion 106A of the reaction gas flow path formed directly on the base material are attached, so that less The number of steps to achieve a separator with electrical conductivity, thermal conductivity, air impermeability, rigidity, and reinforcement.
  • a structure, material composition, or mixing ratio similar to that of the anode-side separator 6 and the cathode-side separator 7 can be applied, and a different structure, material composition, or mixing ratio can also be applied.
  • the same conductive flexible film material is used as the two substrates, but the anode-side substrate and the cathode-side substrate may be different kinds of substrates.
  • the separators of the first to third embodiments of the present invention are composed of two separator base materials 100, a cooling medium flow path 21 formed by an adhesion method, and/or a reaction gas flow path 22 formed by an adhesion method
  • the separator can therefore achieve the effects described below.
  • two separator substrates 100 using more than one conductive flexible membrane material are laminated together, and a conductive and thermally conductive separator is used between them.
  • a cooling medium flow path 21 formed of a functional material By adopting a fluid guiding flow path formed by the separator substrate 100 with high electrical and thermal conductivity and an adhesive material, a separator with stable electrical and thermal conductivity can be obtained.
  • the reinforcement effect of the ribs 11 of the cooling medium flow path formed between the two separator base materials 100 can increase the specific rigidity of the separator.
  • a separator substrate 100 that is thinner in the range of 10 to 100 ⁇ m is used, and the fluid guiding flow path is attached to the substrate, thereby suppressing individual cells of the fuel cell.
  • the thickness of the fuel cell stack is reduced, and the stacking interval (cell pitch) of the fuel cell stack is shortened.
  • a fuel cell with thinner thickness/light weight, high power output volume density, and high power output weight density is realized.
  • the same or different materials as the ribs 11 and 12 are used to form a reinforcement layer and a frame.
  • the structure of the fluid guiding flow path can improve the adhesion and adhesion between the thin separator substrate 100 and the ribs of the flow path, which has conductivity, thermal conductivity, air impermeability, and corrosion resistance, and uses various patterns
  • the shaped flow channel ribs strengthen the separator substrate 100, and can improve the rigidity and strengthening of the separator.
  • the reaction gas flow path 22 when the reaction gas flow path 22 is attached to the surface of the gas diffusion layer 4, 5, the two base materials are bonded together to form the cooling medium flow path 21
  • the main body of the separator can be a common separator suitable for both the anode side and the cathode side, and the freedom of assembly can be improved.
  • the fuel cell separator since the air-impermeable flexible membrane substrate is used as the base, the reactant gases flowing through adjacent flow paths will not be mixed, and it has a high gas barrier. And it has high flexibility that can effectively absorb stress.
  • this flexible separator for fuel cells, it can alleviate the internal stress concentration and corrosion of the MEA caused by the thermal expansion inside the battery cell during power generation. stress.
  • the effect of absorbing displacement without affecting the inside of the battery cell can be obtained. In other words, when assembling the fuel cell stack, it can be flexibly deformed to prevent inappropriate surface pressure distribution, making handling easier.
  • thermal durability/reliability and mechanical durability/reliability in a highly active reaction environment can be improved, and battery life can be improved.
  • a highly conductive carbon composite flexible membrane material is used for the separator substrate 100.
  • the highly conductive carbon composite flexible membrane material is composed of a conductive carbon material, a resin composition, and a conductive carbon reinforcement material.
  • a separator with stronger corrosion resistance than a metal separator can be obtained.
  • fine graphite fibers and/or carbon nanotubes and/or graphene during the molding of the separator substrate 100, the rigidity, conductivity, thermal conductivity, and gas impermeability of the separator substrate 100 can be improved.
  • the contact resistance and interface with the surface of the separator substrate 100 can be improved. Heat conduction and other properties.
  • a highly conductive adhesive material is used as the material for the fluid guiding flow path attached to the separator base 100.
  • the fine graphite fibers, carbon nanotubes, graphene, other materials or combinations thereof contained in the attachment material are used as the first material, and are entangled with the conductive resin as the second material, which can improve the conductivity of the ribs 11, 12, Mechanical strength and heat resistance strength can impart deterioration of heat resistance and rigidity/reinforcement of separators.
  • the fuel cell separator of the present invention by combining a roll-to-roll method capable of winding various substrates into a roll, and a technique that utilizes an adhesion technology to directly attach the fluid guide flow path to the substrate, it is possible to achieve Lower cost realizes thinner, lighter, and bendable properties. Since the adhering fluid guide flow path is formed independently of the base material, a mold for forming the metal separator flow path is not required, and the effect of being able to easily cope with the flow path design accompanying the specification change can be obtained at a lower cost.
  • the manufacturing method and its processes are based on the design specifications of the separator, and are produced from each base material [1], cutting process [2], surface treatment process [3], and strengthening layer Formation step [4], cooling medium flow path formation step [5], bonding step [6], pressure heating treatment step [7], reaction gas flow path formation step [8], a total of 8 steps are constructed, because All components can be formed using a two-dimensional processing method using adhesion, so it has the effect of being able to quickly respond to fine adjustments associated with specification changes.
  • the method of attaching the ribs 11, 12 made of a dense carbon-based material or a porous carbon-based material uses coating, printing, and dots.
  • Glue, spray, and transfer methods are suitable for roll-to-roll production methods, so production costs can be saved and higher productivity can be achieved.
  • the precursor of the adhesion material is prepared by mixing one or more conductive materials and/or conductive composite materials, one or more adhesive resins, one or more dispersing solvents, other additives, other substances, and the like. With this method, a variety of attachment materials can be easily prepared, and mass production can be carried out at a lower cost.
  • corona treatment, low-temperature plasma treatment, chemical treatment, solvent treatment, and other appropriate treatments are used as the surface of the separator substrate 100 using a conductive flexible membrane material.
  • the pre-modification treatment method can prevent the surface of the substrate from being corroded, and can enhance the adhesion and adhesion between the separator substrate 100 and the fluid guiding flow path.
  • the surface treatment layer 105 by providing the surface treatment layer 105 with an inclined functional structure that makes the carbon component density of the reinforcing layer 106 higher than the base material side, the internal stress can be reduced and the base material can be prevented. Or the bending of other material layers prevents cracks from occurring, and it is difficult to produce interface peeling.
  • the cooling medium flow path 21 is formed on the surface of the separator substrate made of a conductive flexible membrane material, and it is possible to obtain high conductivity, high thermal conductivity, and high conductivity.
  • a separator with gas barrier and corrosion resistance By using the above-mentioned thinner, lighter, and flexible separator to construct a fuel cell unit, a fuel cell with high output power volume density, high output power weight density and high reliability can be obtained.
  • due to the application of the roll-to-roll production method it can realize the processing of the roll-shaped substrate with thinner, lighter, and bendable properties, which can achieve significant productivity and cost in the low-cost mass production process. To improve.
  • the fuel cell separator according to the present invention can stably supply the cooling medium and reaction gas.
  • the fuel cell stack according to the present invention can ensure stable power generation performance, so it can also be applied to portable power supplies and portability. Power supplies for equipment, power supplies for electric vehicles, etc.
  • the fuel cell of the present invention can be used as an automotive fuel cell. Among them, in addition to cars, it can also be used for batteries for drones and airplanes.
  • the present invention is not limited to the above-mentioned embodiments, and can be implemented in various configurations within the scope not departing from the gist thereof.
  • the technical features of the embodiments described in the specification of the present invention can be appropriately substituted or combined in order to solve some or all of the above-mentioned problems and effects.

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Abstract

A separator plate (6, 7) for a fuel cell. The separator plate (6, 7) comprises a pair of separator plate substrates (100), and the separator plate substrate (100) is a conductive carbon composite flexible membrane material. A cooling medium flow path (21) is provided between the pair of separator plate substrates (100). The present invention further provides a manufacturing method for the separator plate (6, 7) for the fuel cell, and the fuel cell using the separator plate (6, 7).

Description

燃料电池用的隔板、制造方法以及使用该隔板的燃料电池Separator for fuel cell, manufacturing method and fuel cell using the separator 技术领域Technical field
本发明涉及燃料电池用隔板，具体涉及一种在作为导电性柔性膜材的2个基材间附着(Adhere)有冷却介质流路的燃料电池用的隔板，这种隔板能用于固体高分子型等燃料电池。The present invention relates to a fuel cell separator, in particular to a fuel cell separator with a cooling medium flow path attached (Adhere) between two base materials as a conductive flexible membrane material. This separator can be used for Solid polymer fuel cell.
背景技术Background technique
燃料电池一般被用于将多个燃料电池单个单元串联连接构成的燃料电池堆。使用组装装置，在恰当定位的同时，通过层叠端板、集电板、绝缘板、隔板、电解质膜接合体等构成部件来进行燃料电池堆的组装。作为燃料电池的一种，已知有使用氢离子透过性的固体高分子电解质膜的固体高分子型燃料电池。固体高分子型燃料电池的单个单元具备夹持高分子膜的一对气体扩散层，在各气体扩散层的外侧配置有隔板。Fuel cells are generally used in a fuel cell stack constructed by connecting multiple fuel cell units in series. The assembly device is used to assemble the fuel cell stack by stacking components such as end plates, current collector plates, insulating plates, separators, and electrolyte membrane assemblies while properly positioned. As a type of fuel cell, a solid polymer fuel cell using a hydrogen ion-permeable solid polymer electrolyte membrane is known. A single cell of a solid polymer fuel cell includes a pair of gas diffusion layers sandwiching a polymer membrane, and separators are arranged on the outside of each gas diffusion layer.
固体高分子型燃料电池的构成部件中的隔板由具有导电性的板状构件形成。在该隔板上形成有氧化气体流路、燃料气体流路以及冷却介质流路。具体而言，在隔板的一个面上，形成有氧化气体流路或燃料气体流路。冷却介质流路形成在隔板的另一个面上。The separator in the component parts of the polymer electrolyte fuel cell is formed of a conductive plate-shaped member. An oxidizing gas flow path, a fuel gas flow path, and a cooling medium flow path are formed on the separator. Specifically, an oxidizing gas flow path or a fuel gas flow path is formed on one surface of the separator. The cooling medium flow path is formed on the other surface of the partition.
即，多个电池单元层叠并紧固而形成堆组的燃料电池隔板，是由2个板状构件接合组成的。在一个板状构件的外表面形成有燃料气体流路，在另一个板状构件的外表面形成有氧化气体流路。在位于接合的2个板状构件的内侧的内表面上，形成有冷却介质流路。In other words, the fuel cell separator in which a plurality of battery cells are stacked and fastened to form a stack is composed of two plate-shaped members joined together. A fuel gas flow path is formed on the outer surface of one plate-shaped member, and an oxidizing gas flow path is formed on the outer surface of the other plate-shaped member. A cooling medium flow path is formed on the inner surface located inside the two plate-shaped members to be joined.
一般，隔板具有作为隔开单个电池单元与单个电池单元间的分隔壁的作用，以及起到如下作用：即，传输产生的电子的导电体、提供空气和氢气并排出生成水或气体的流路。为了使固体高分子型燃料电池实用化，需要使用有足够的导电性并能将反应热释放到外部的热传导性优异的隔板。此外，根据运输设备的空间和运输距离的限制、节省资源或运输成本的问题，需要更薄型且重量较轻的隔板。另外，由于隔板较厚会引起内部电阻增大，因此隔板不能过厚。Generally, the separator has a role as a partition wall separating a single battery cell from a single battery cell, and has the following functions: that is, a conductor that transmits the generated electrons, provides air and hydrogen, and discharges the flow of water or gas. road. In order to make a solid polymer fuel cell practical, it is necessary to use a separator with sufficient conductivity and excellent thermal conductivity that can release reaction heat to the outside. In addition, according to the limitation of the space and transportation distance of transportation equipment, resource saving or transportation cost issues, thinner and lighter partitions are required. In addition, since the thickness of the separator will increase the internal resistance, the separator cannot be too thick.
在当前燃料电池的领域中，主流趋势是在金属表面形成槽形形状的流体引 导流路的金属隔板。例如，在被多次提出的金属隔板中，根据专利文献1中的金属隔板，为了在其表面形成流路，包含对隔板自身进行成型的工序，金属的冲压、金属的切削、对隔板的外形进行修型、去除污染成分的工序，表面膜形成工序以及其他等等制造工序数量繁多，生产成本高。而且，金属制的基材是难以进行模具加工的较硬的材料，因此单件产品生产时间(Tact time)提高。金属存在以下各种问题：金属加工需要昂贵的设备投资，费用昂贵，材料成本价格也高，而且其加工需要较长的步骤，并且容易发生破损、折皱或弯曲变形等，缺乏材料的柔软性等。In the current fuel cell field, the mainstream trend is to form a metal separator with a groove-shaped fluid guide flow path on the metal surface. For example, among the metal separators that have been proposed many times, according to the metal separator in Patent Document 1, in order to form a flow path on its surface, the separator itself includes the steps of forming the separator itself, such as metal pressing, metal cutting, and The process of repairing the shape of the separator and removing contaminants, the surface film forming process and other manufacturing processes are numerous, and the production cost is high. In addition, metal substrates are harder materials that are difficult to mold, so the production time of a single product (Tact time) is increased. Metal has the following problems: metal processing requires expensive equipment investment, high cost, and high material cost, and its processing requires a long step, and it is prone to breakage, wrinkles or bending deformation, etc., and lacks material flexibility, etc. .
此外，根据专利文献2提出的树脂隔板，其是在导电性树脂板的两面上层叠复合柔性膜材来构成。这里提出的树脂隔板与金属隔板相比化学性较稳定且耐腐蚀性优异，加工性优异，但是与金属隔板相比接触电阻值较高，因此导电性较差。此外，在高分子树脂中热量通过振动来传递，因此示出比金属要低几个数量级的热传导率。也就是说，为了使电子顺畅地移动需要改善树脂隔板的导电性，同时还要求改善其热传导性。In addition, according to the resin separator proposed in Patent Document 2, a composite flexible film material is laminated on both sides of a conductive resin plate. Compared with the metal separator, the resin separator proposed here is chemically more stable and excellent in corrosion resistance, and is excellent in processability. However, compared with the metal separator, the contact resistance value is higher, and therefore the conductivity is poor. In addition, in the polymer resin, heat is transferred by vibration, and therefore shows a thermal conductivity that is several orders of magnitude lower than that of metal. In other words, in order to allow electrons to move smoothly, it is necessary to improve the conductivity of the resin separator, and it is also required to improve its thermal conductivity.
现有技术文献Prior art literature
专利文献Patent literature
专利文献1：日本专利特开2006－294335号公报Patent Document 1: Japanese Patent Laid-Open No. 2006-294335
专利文献2：日本专利特开2016－119181号公报Patent Document 2: Japanese Patent Laid-Open No. 2016-119181
发明内容Summary of the invention
发明所要解决的技术问题The technical problem to be solved by the invention
与专利文献1的金属隔板相比，专利文献2所公开的树脂隔板的导电性/热传导性不足，从提高电气特性及热特性的观点出发还有改善的余地。专利文献1的金属隔板与专利文献2的树脂隔板相比具有优异的导电性，但是针对金属腐蚀问题，为了防止由于在化学反应后产生的生成水导致的腐蚀，需要形成钝化涂层等来提高金属隔板的耐腐蚀性。金属隔板相对比树脂隔板较薄，但二者都需薄型化以提高功率密度。此外，从提高生产性的观点出发，卷对卷(roll to roll)方式的生产方法难以适用于对流体引导流路进行冲压成型或印刻的一体型的金属隔板。Compared with the metal separator of Patent Document 1, the resin separator disclosed in Patent Document 2 has insufficient electrical conductivity and thermal conductivity, and there is room for improvement from the viewpoint of improving electrical characteristics and thermal characteristics. The metal separator of Patent Document 1 has superior electrical conductivity compared to the resin separator of Patent Document 2, but in order to prevent corrosion due to water generated after a chemical reaction, it is necessary to form a passivation coating for the problem of metal corrosion. Etc. to improve the corrosion resistance of the metal separator. Metal separators are relatively thinner than resin separators, but both need to be thinner to increase power density. In addition, from the viewpoint of improving productivity, a roll-to-roll production method is difficult to be applied to an integrated metal separator that is press-formed or imprinted on a fluid guiding flow path.
本发明的目的之一是提供一种燃料电池用的隔板，该隔板可以保持足够的刚性并且比金属隔板的厚度更薄。在一些示例中，该隔板具备优异的导电性、热传导性、不透气性、耐腐蚀性和低接触电阻。本发明还提供该燃料电池用的隔板的制造方法以及使用该隔板的燃料电池，进而能提高燃料电池的发电性能、使单个电池单元薄型化、有助于实现燃料电池的高功率密度化、小型化或轻量化，能以良好的加工性提高操作性，能以卷对卷方式进行低成本生产以满足市场的需求。One of the objects of the present invention is to provide a separator for a fuel cell, which can maintain sufficient rigidity and is thinner than a metal separator. In some examples, the separator has excellent electrical conductivity, thermal conductivity, gas impermeability, corrosion resistance, and low contact resistance. The present invention also provides a method for manufacturing the fuel cell separator and a fuel cell using the separator, thereby improving the power generation performance of the fuel cell, reducing the thickness of a single cell, and contributing to the realization of high power density of the fuel cell , Miniaturization or light weight, can improve operability with good processability, and can be produced at low cost in roll-to-roll mode to meet market demand.
本发明的一个方面使用能赋予导电性、热传导性、不透气性、耐腐蚀性、刚性、强化性、柔性的材料来形成隔板，使燃料电池在具有上述特性的同时提高燃料电池的发电性能(高输出功率体积密度、高输出功率重量密度、较高的可靠性)。One aspect of the present invention uses materials that can impart electrical conductivity, thermal conductivity, gas impermeability, corrosion resistance, rigidity, reinforcement, and flexibility to form the separator, so that the fuel cell has the above characteristics while improving the power generation performance of the fuel cell (High output power volume density, high output power weight density, higher reliability).
具体而言，本发明的一个方面通过在具有足够的导电性/热传导性，具备不透气性/耐腐蚀性，具备容易进行加工的性质的柔性的基材(柔性膜材)上，伴随有形成流体引导流路，从而提供一种具有导电性、热传导性、不透气性、耐腐蚀性、刚性、强化性、柔性的隔板以及使用该隔板的固体高分子型燃料电池。进而，本发明的目标是为了应对燃料电池的高功率密度和小型化/轻量化，使燃料电池用的隔板的结构实现厚度极薄且具有柔性(容易加工、应力难以集中、可靠性提高)，并且可以利用低成本的卷对卷方式进行量产。Specifically, one aspect of the present invention is formed on a flexible substrate (flexible film) that has sufficient electrical conductivity/thermal conductivity, airtightness/corrosion resistance, and is easy to process. The fluid guides the flow path, thereby providing a separator having conductivity, thermal conductivity, gas impermeability, corrosion resistance, rigidity, reinforcement, and flexibility, and a solid polymer fuel cell using the separator. Furthermore, the object of the present invention is to cope with the high power density and miniaturization/weight reduction of fuel cells, and to realize the structure of fuel cell separators with extremely thin thickness and flexibility (easy to process, hard to concentrate stress, and improved reliability). , And can use low-cost roll-to-roll method for mass production.
解决技术问题的技术方案Technical solutions to solve technical problems
本发明为了实现上述目的，提供按下述方式构成的燃料电池用的隔板。本发明的一个方面提供一种燃料电池用的隔板，包括相对设置的一对隔板基材，所述隔板基材是导电性碳复合柔性膜材；以及布置在所述一对隔板基材之间的冷却介质流路。In order to achieve the above-mentioned object, the present invention provides a separator for a fuel cell constructed in the following manner. One aspect of the present invention provides a separator for a fuel cell, comprising a pair of separator substrates arranged oppositely, the separator substrate being a conductive carbon composite flexible membrane material; and the separator is arranged on the pair of separators The cooling medium flow path between the substrates.
根据本发明的一个方面，还包括布置在所述隔板基材的外侧的反应气体流路。According to an aspect of the present invention, it further includes a reactive gas flow path arranged on the outer side of the separator substrate.
根据本发明的一个方面，还包括覆盖所述隔板基材表面的具有如下至少一种特性的表面处理层和/或表面改质层：表面耐腐蚀性、界面接合性和界面密接性。According to one aspect of the present invention, it further includes a surface treatment layer and/or a surface modification layer covering the surface of the separator substrate and having at least one of the following characteristics: surface corrosion resistance, interface adhesion, and interface adhesion.
根据本发明的一个方面，还包括覆盖所述表面处理层和/或表面改质层的用 于提高刚性的强化层。According to an aspect of the present invention, it further includes a strengthening layer for increasing rigidity covering the surface treatment layer and/or the surface modification layer.
根据本发明的一个方面，所述冷却介质流路形成在所述隔板基材上、所述表面处理层上、所述表面改质层上或所述强化层上。According to one aspect of the present invention, the cooling medium flow path is formed on the separator substrate, the surface treatment layer, the surface modification layer, or the reinforcement layer.
根据本发明的一个方面，还包括布置在隔板基材的外侧的反应气体流路，所述反应气体流路形成在所述隔板基材至少其中之一上、所述表面处理层上、所述表面改质层上或所述强化层上。According to one aspect of the present invention, it further includes a reactive gas flow path arranged on the outside of the separator substrate, the reactive gas flow path being formed on at least one of the separator substrates, on the surface treatment layer, On the surface modification layer or on the strengthening layer.
根据本发明的一个方面，所述隔板基材是包括至少一种导电性材料以及至少一种树脂组成物。According to one aspect of the present invention, the separator substrate includes at least one conductive material and at least one resin composition.
根据本发明的一个方面，所述隔板基材还包括至少一种导电性强化材料。According to one aspect of the present invention, the separator substrate further includes at least one conductivity enhancing material.
根据本发明的一个方面，所述导电性强化材料包括细石墨纤维、碳纳米管和/或石墨烯。According to one aspect of the present invention, the conductive reinforcing material includes fine graphite fibers, carbon nanotubes and/or graphene.
根据本发明的一个方面，所述导电性强化材料垂直于所述隔板基材的延伸面排列或相对于隔板基材的延伸面倾斜排列。According to one aspect of the present invention, the conductive reinforcing material is arranged perpendicular to the extension surface of the separator substrate or arranged obliquely with respect to the extension surface of the separator substrate.
根据本发明的一个方面，所述冷却介质流路和/反应气体流路的附着材料包括致密性的碳基材料和/或多孔碳基材料。According to one aspect of the present invention, the attachment material of the cooling medium flow path and/or the reaction gas flow path includes a dense carbon-based material and/or a porous carbon-based material.
根据本发明的一个方面，在所述反应气体流路的全部或局部区域中附着亲水性镀膜液、疏水性镀膜液或防水性镀膜液，或者仅在所述反应气体流路的沟道部的底部附着亲水性镀膜液。According to one aspect of the present invention, a hydrophilic coating solution, a hydrophobic coating solution, or a water-repellent coating solution is attached to all or a partial area of the reaction gas flow path, or only in the channel portion of the reaction gas flow path. Hydrophilic coating solution is attached to the bottom of the tube.
根据本发明的一个方面，所述隔板基材的厚度在10～200μm的范围内。According to one aspect of the present invention, the thickness of the separator substrate is in the range of 10 to 200 μm.
根据本发明的一个方面，所述表面处理层的厚度在1～1,000nm的范围内。According to an aspect of the present invention, the thickness of the surface treatment layer is in the range of 1 to 1,000 nm.
根据本发明的一个方面，所述表面改质层的厚度在0.1～1,000nm的范围内。According to an aspect of the present invention, the thickness of the surface modification layer is in the range of 0.1 to 1,000 nm.
根据本发明的一个方面，所述强化层的厚度在1～50μm的范围内。According to one aspect of the present invention, the thickness of the strengthening layer is in the range of 1-50 μm.
根据本发明的一个方面，所述冷却介质流路和/或反应气体流路的高度在1～500μm的范围内。According to one aspect of the present invention, the height of the cooling medium flow path and/or the reaction gas flow path is in the range of 1 to 500 μm.
根据本发明的一个方面，所述隔板的厚度在10～1,000μm的范围内。According to an aspect of the present invention, the thickness of the separator is in the range of 10 to 1,000 μm.
本发明还提供一种燃料电池，包括多个膜电极接合体以及多个如前所述的隔板，每一膜电极接合体布置于相邻的隔板之间。The present invention also provides a fuel cell, including a plurality of membrane electrode assemblies and a plurality of separators as described above, each membrane electrode assembly being arranged between adjacent separators.
根据本发明的一个方面，所述膜电极接合体包括催化剂涂覆膜和分别设于所述催化剂涂覆膜的第一侧和第二侧的气体扩散层。According to an aspect of the present invention, the membrane electrode assembly includes a catalyst coating film and gas diffusion layers respectively provided on the first side and the second side of the catalyst coating film.
根据本发明的一个方面，在所述隔板基材一侧和/或与所述隔板基材相对的气体扩散层一侧，布置有反应气体流路。According to one aspect of the present invention, a reactive gas flow path is arranged on the side of the separator substrate and/or the side of the gas diffusion layer opposite to the separator substrate.
本发明还提供一种燃料电池用的隔板的制造方法，包括以下步骤：提供为导电性碳复合柔性膜材的一对隔板基材；在所述一对隔板基材的至少一个隔板基材的一侧附着冷却介质流路；贴合所述一对隔板基材，其中所述冷却介质流路位于所述一对隔板基材之间。The present invention also provides a method for manufacturing a separator for a fuel cell, which includes the following steps: providing a pair of separator substrates as conductive carbon composite flexible membrane materials; at least one separator of the pair of separator substrates A cooling medium flow path is attached to one side of the plate base material; the pair of separator base materials are bonded together, wherein the cooling medium flow path is located between the pair of separator base materials.
根据本发明的一个方面，在贴合所述一对隔板基材后，还包括对所述一对隔板基材进行加压和/或加热。According to one aspect of the present invention, after bonding the pair of separator substrates, the method further includes pressurizing and/or heating the pair of separator substrates.
根据本发明的一个方面，还包括在所述一对隔板基材的至少一个隔板基材的表面形成表面处理层和/或表面改质层，所述表面处理层和/或表面改质层具有如下至少一种特性：表面耐腐蚀性、界面接合性和界面密接性。According to one aspect of the present invention, it further includes forming a surface treatment layer and/or a surface modification layer on the surface of at least one separator substrate of the pair of separator substrates, the surface treatment layer and/or surface modification The layer has at least one of the following characteristics: surface corrosion resistance, interface adhesion, and interface adhesion.
根据本发明的一个方面，还包括在所述一对隔板基材的至少一个隔板基材的表面形成用于提高刚性的强化层。According to one aspect of the present invention, the method further includes forming a reinforcing layer for improving rigidity on the surface of at least one separator substrate of the pair of separator substrates.
根据本发明的一个方面，还包括在所述一对隔板基材的至少一个隔板基材的非贴合侧附着反应气体流路。According to an aspect of the present invention, it further includes a reaction gas flow path attached to the non-bonding side of at least one separator substrate of the pair of separator substrates.
根据本发明的一个方面，还包括在所述反应气体流路的全部或局部区域涂布亲水性涂料液或防水性涂料液。According to one aspect of the present invention, the method further includes coating a hydrophilic coating liquid or a waterproof coating liquid on all or a partial area of the reaction gas flow path.
根据本发明的一个方面，提供所述一对隔板基材的方法包括：层叠导电性材料、导电性强化材料和树脂组成物以形成层叠体；使用具有弹性的膜覆盖所述层叠体；加压和/或加热所述层叠体以使所述层叠体硬化。According to one aspect of the present invention, a method of providing the pair of separator substrates includes: laminating a conductive material, a conductive reinforcing material, and a resin composition to form a laminated body; covering the laminated body with a film having elasticity; adding The laminate is pressed and/or heated to harden the laminate.
根据本发明的一个方面，所述表面处理层的材料包括：与构成所述冷却介质流路的肋部的材料相同的材料；或碳组分的总计含有率从所述隔板基材侧向外侧变高的倾斜功能结构的材料。According to one aspect of the present invention, the material of the surface treatment layer includes: the same material as that of the ribs constituting the cooling medium flow path; or the total content of carbon component is from the side of the separator substrate The material of the inclined functional structure that the outer side becomes higher.
根据本发明的一个方面，所述冷却介质流路和/或反应气体流路的附着材料包括相互缠绕的第一材料和第二材料，所述第一材料包括细碳纤维、碳纳米管、石墨烯或其组合，所述第二材料包括导电性树脂。。According to an aspect of the present invention, the attachment material of the cooling medium flow path and/or the reaction gas flow path includes a first material and a second material that are entangled with each other, and the first material includes fine carbon fibers, carbon nanotubes, and graphene. Or a combination thereof, the second material includes a conductive resin. .
根据本发明的一个方面，所述冷却介质流路和/或反应气体流路的附着方法包括涂布、印刷、点胶、喷射和转印。According to one aspect of the present invention, the attachment method of the cooling medium flow path and/or the reaction gas flow path includes coating, printing, glue dispensing, spraying and transfer printing.
本发明提供一种燃料电池用的隔板，该隔板将提高了导电性/热传导性的片 状的结构体作为基底基材，在基材的一个面形成提高了导电性/热传导性的冷却介质流路和/或在基材的另一个面形成提高了导电性/热传导性的反应气体流路，由此能实现燃料电池的高导电性、高热传导性、高输出功率体积密度和高输出功率重量密度。除了导电性/热传导性等特性以外，通过使用难腐蚀的功能材料将流体引导流路附着于基材表面，能确保燃料电池堆整体的导电路径和散热路径，并且能有助于防止腐蚀发展。此外，通过同时将流体引导流路附着于基材的表面，还能使隔板具有刚性、强化性。进而，通过使用厚度较薄的基材，能抑制燃料电池单个单元的厚度，能缩短燃料电池堆的层叠间隔(单元间距)。与使用金属隔板的堆组相比，能实现更薄型化/轻量化，获得高输出功率体积密度和高输出功率重量密度的燃料电池。The present invention provides a separator for a fuel cell. The separator uses a sheet-like structure with improved electrical conductivity/thermal conductivity as a base substrate, and a cooling element with improved electrical conductivity/thermal conductivity is formed on one surface of the substrate. The medium flow path and/or the reaction gas flow path with improved electrical conductivity/thermal conductivity is formed on the other surface of the substrate, thereby achieving high electrical conductivity, high thermal conductivity, high output volume density and high output of the fuel cell Power weight density. In addition to properties such as electrical conductivity and thermal conductivity, the use of non-corrosive functional materials to attach the fluid guiding flow path to the surface of the substrate can ensure the entire conductive path and heat dissipation path of the fuel cell stack and help prevent corrosion from developing. In addition, by simultaneously attaching the fluid guide flow path to the surface of the base material, the separator can be made rigid and strengthened. Furthermore, by using a thinner base material, the thickness of a single fuel cell unit can be suppressed, and the stacking interval (cell pitch) of the fuel cell stack can be shortened. Compared with stacks using metal separators, it can achieve thinner/lighter weight, and obtain a fuel cell with high output power volume density and high output power weight density.
本发明利用具有导电性/热传导性的基材和在该基材的表面提供导电性/热传导性的功能材料来形成流体引导流路的协同效应，能进一步提高隔板的导电性和热传导性。通过在相邻的隔板之间和隔板与气体扩散层之间，形成具有导电性/热传导性的流体引导流路，能提供从一个基材连接到另一个基材的导电路径和散热路径。此外，通过将作为燃料电池的构成部件的隔板或气体扩散层作为基底基材来形成流体引导流路，有助于使单元厚度变薄。此外，在相邻的隔板之间形成冷却介质流路(包含流路肋部、强化层)，在隔板的外侧形成反应气体流路，还能获得兼具对厚度较薄的基材强化的框架结构的作用，能提高隔板的刚性、强化性。The present invention utilizes a conductive/thermal conductive substrate and a functional material providing conductivity/thermal conductivity on the surface of the substrate to form a synergistic effect of fluid guiding flow paths, which can further improve the conductivity and thermal conductivity of the separator. By forming a conductive/thermally conductive fluid guide flow path between adjacent separators and between the separator and the gas diffusion layer, it is possible to provide a conductive path and a heat dissipation path connecting one substrate to another substrate . In addition, forming a fluid guide flow path by using a separator or a gas diffusion layer as a component of a fuel cell as a base substrate contributes to making the cell thickness thin. In addition, a cooling medium flow path (including flow path ribs and a reinforcing layer) is formed between adjacent separators, and a reactive gas flow path is formed on the outside of the separator, which can also achieve a thinner base material reinforcement. The role of the frame structure can improve the rigidity and strengthening of the partition.
附图概述Brief description of the drawings
本发明的特征、性能由以下的实施例及其附图进一步描述。The features and performance of the present invention are further described by the following embodiments and drawings.
图1是表示本发明的一个实施方式中的燃料电池的单个单元的结构示意图。FIG. 1 is a schematic diagram showing the structure of a single unit of a fuel cell in an embodiment of the present invention.
图2A-2C是本发明的一个实施方式中的燃料电池用隔板的一个示例，图2A是隔板的冷却介质流路侧的俯视图，图2B是沿着相当于活性区域的隔板的S-S’线的剖视图，图2C是隔板基材的剖视图。2A-2C are an example of a fuel cell separator in an embodiment of the present invention, FIG. 2A is a plan view of the cooling medium flow path side of the separator, and FIG. 2B is along the S of the separator corresponding to the active region. The cross-sectional view of the line -S', and FIG. 2C is a cross-sectional view of the separator substrate.
图3是本发明的实施方式1所涉及的燃料电池用的隔板的局部剖视图的一个示例。3 is an example of a partial cross-sectional view of a separator for a fuel cell according to Embodiment 1 of the present invention.
图4是本发明的实施方式2所涉及的燃料电池用的隔板的局部剖视图的一个示例。4 is an example of a partial cross-sectional view of a separator for a fuel cell according to Embodiment 2 of the present invention.
图5是本发明的实施方式3所涉及的燃料电池用的隔板的局部剖视图。5 is a partial cross-sectional view of a separator for a fuel cell according to Embodiment 3 of the present invention.
图6是本发明的一个实施方式中的附着于固体高分子型燃料电池用的隔板的流体引导流路的平面图案的示例图。Fig. 6 is a diagram showing an example of a planar pattern of a fluid guiding flow path attached to a separator for a polymer electrolyte fuel cell in an embodiment of the present invention.
图7是用于说明本发明的一个实施方式中的隔板的制造方法的示例性流程图。Fig. 7 is an exemplary flowchart for explaining a method of manufacturing a separator in an embodiment of the present invention.
标号说明Label description
1  高分子电解质膜1 Polymer electrolyte membrane
2  阳极侧催化剂层2 Anode side catalyst layer
3  阴极侧催化剂层3 Cathode side catalyst layer
4  阳极侧气体扩散层4 Gas diffusion layer on the anode side
5  阴极侧气体扩散层5 Gas diffusion layer on the cathode side
6  阳极侧隔板6 Anode side separator
7  阴极侧隔板7 Cathode side separator
11、12  肋部11, 12 Ribs
100  隔板基材100 Separator substrate
101  第一隔板基材101 First separator substrate
102  第二隔板基材102 Second separator substrate
105  表面处理层、表面改质层105 Surface treatment layer, surface modification layer
106  强化层106 Strengthening layer
106A  强化部106A Strengthening Department
20  密封材料20 Sealing material
21  冷却介质流路21 Cooling medium flow path
22  反应气体流路22 Reactive gas flow path
本发明的较佳实施方式Preferred embodiment of the present invention
以下参考附图，基于本发明的实施方式对本发明进行详细说明，下面的实施方式1～3所示出的结构、材料、处理内容、处理步骤等只要不脱离本发明的主旨即可以适当进行变更，本发明完全不受实施方式的限制。Hereinafter, the present invention will be described in detail based on the embodiments of the present invention with reference to the drawings. The structures, materials, processing contents, processing procedures, etc. shown in the following Embodiments 1 to 3 can be appropriately modified as long as they do not depart from the gist of the present invention. , The present invention is not limited by the embodiment at all.
下面参考各附图说明本发明的实施方式1～3。在下面的附图中，对相同或相 当的部分标注相同的参考标号且不重复其说明。为了方便说明，适当夸张地表现各附图。请注意，这些附图的尺寸比率为了便于说明而被夸张，有时与实际的比率不同，不是正确的比例尺，示出的可能比实际要大。另外，本发明的实施方式举例示出对本发明的技术思想进行具体化的结构，实施方式中各部分的材质、形状、结构、配置、尺寸等并非必须特定为如下内容。本发明的技术思想在权利要求书中所记载的权利要求所规定的技术范围内，可以进行各种变更。Hereinafter, Embodiments 1 to 3 of the present invention will be described with reference to the drawings. In the following drawings, the same or equivalent parts are given the same reference numerals and their descriptions are not repeated. For the convenience of description, each drawing is shown exaggeratedly. Please note that the dimensional ratios of these drawings are exaggerated for the convenience of explanation, and sometimes differ from the actual ratios, and are not the correct scales, and the shown may be larger than actual. In addition, the embodiment of the present invention exemplifies a structure that embodies the technical idea of the present invention, and the material, shape, structure, arrangement, size, etc. of each part in the embodiment are not necessarily specified as follows. The technical idea of the present invention can be variously changed within the technical scope defined by the claims described in the claims.
首先，对使用了能适用于实施本发明的具体实施方式的膜电极接合体的固体高分子型燃料电池进行说明。作为一个示例，图1是表示本发明的实施方式1～3所涉及的固体高分子型燃料电池的单个单元的结构示意图。First, a polymer electrolyte fuel cell using a membrane electrode assembly applicable to specific embodiments of the present invention will be described. As an example, FIG. 1 is a schematic diagram showing the structure of a single unit of a polymer electrolyte fuel cell according to Embodiments 1 to 3 of the present invention.
(燃料电池的整体结构)(The overall structure of the fuel cell)
如图1所示，本实施方式所涉及的固体高分子型燃料电池包括多个膜电极接合体MEA(Membrane Electrode Assembly)。对于一个膜电极接合体MEA来说，包括高分子电解质膜1、两个催化剂层2、3以及两个气体扩散层4、5，分别构成阳极和阴极。其中，高分子电解质膜1的两个面上以CCM(Catalyst Coated Membrane)方式涂覆了催化剂涂层膜，该催化剂涂层膜的第一侧和第二侧分别对应于催化剂层2和催化剂层3。在该膜电极接合体MEA的一侧面配置阳极电极构成电池的阳极，另一侧面配置阴极电极构成电池的阴极。膜电极接合体MEA夹设在两组隔板6、7之间。隔板6、7起到隔开单个单元间的分隔板的作用。As shown in FIG. 1, the polymer electrolyte fuel cell according to this embodiment includes a plurality of membrane electrode assemblies MEA (Membrane Electrode Assembly). A membrane electrode assembly MEA includes a polymer electrolyte membrane 1, two catalyst layers 2, 3, and two gas diffusion layers 4, 5, which constitute an anode and a cathode, respectively. Among them, the two sides of the polymer electrolyte membrane 1 are coated with a catalyst coating membrane in a CCM (Catalyst Coated Membrane) manner. The first side and the second side of the catalyst coating membrane correspond to the catalyst layer 2 and the catalyst layer, respectively. 3. An anode electrode is arranged on one side surface of the membrane electrode assembly MEA to constitute the anode of the battery, and the cathode electrode is arranged on the other side surface to constitute the cathode of the battery. The membrane electrode assembly MEA is sandwiched between the two sets of separators 6 and 7. The partitions 6, 7 function as partitions separating individual units.
如图1所示，根据本发明的一个实施方式所涉及的燃料电池，是在一组隔板6、7中夹持膜电极接合体MEA的所谓单个单元结构的固体高分子型燃料电池。其中，一组隔板6、7包括阳极侧隔板6和阴极侧隔板7。相应地，催化剂层2为阳极侧催化剂层2，催化剂层3为阴极侧催化剂层3，气体扩散层4为阳极侧气体扩散层4，气体扩散层5为阴极侧气体扩散层5。本发明的实施方式采用经由隔板6、7串联地层叠多个电池单元的堆组结构。虽然省略图示，但燃料电池堆是将多个电池单元层叠形成层叠体，在该层叠体的两端按照集电板、绝缘板以及端板的顺序配置来构成的。As shown in FIG. 1, the fuel cell according to one embodiment of the present invention is a so-called single-cell structure polymer electrolyte fuel cell in which a membrane electrode assembly MEA is sandwiched between a set of separators 6 and 7. Among them, a set of separators 6 and 7 includes an anode-side separator 6 and a cathode-side separator 7. Correspondingly, the catalyst layer 2 is the anode side catalyst layer 2, the catalyst layer 3 is the cathode side catalyst layer 3, the gas diffusion layer 4 is the anode side gas diffusion layer 4, and the gas diffusion layer 5 is the cathode side gas diffusion layer 5. The embodiment of the present invention adopts a stack structure in which a plurality of battery cells are stacked in series via separators 6 and 7. Although not shown, the fuel cell stack is constructed by stacking a plurality of battery cells to form a laminate, and the current collector plates, insulating plates, and end plates are arranged in this order at both ends of the laminate.
在上述膜电极接合体MEA和隔板6、7之间，沿着进行反应的表面(简称反应面)形成反应气体流路22，在隔开相邻的单个单元的隔板6与隔板7之间形成有冷却介质流路21。而且，在上述隔板6、7的外缘，设置有以气密性/水密性为 目的的密封构件，防止冷却介质、反应气体等泄漏。Between the above-mentioned membrane electrode assembly MEA and the separators 6, 7, a reaction gas flow path 22 is formed along the surface where the reaction proceeds (referred to as the reaction surface), and the separator 6 and the separator 7 that separate adjacent individual cells are formed. A cooling medium flow path 21 is formed therebetween. In addition, sealing members for the purpose of airtightness and watertightness are provided on the outer edges of the above-mentioned partitions 6, 7 to prevent leakage of cooling medium, reaction gas, and the like.
将反应气体流路22和冷却介质流路21统称为流体引导流路。具体而言，在隔板6、7与气体扩散层4、5之间形成各自的反应气体流路22。在隔开相邻的单个单元的隔板6、7之间形成冷却介质流路21。使用例如水、乙二醇等防冻剂、空气等作为冷却介质。如图1所示，从阳极侧隔板6的反应气体流路22提供燃料气体(阳极气体)。燃料气体例如可以是氢气、甲烷气等。从阴极侧隔板7的反应气体流路22提供氧化气体(阴极气体)。氧化气体例如可以是氧气、空气等含氧的气体。The reaction gas flow path 22 and the cooling medium flow path 21 are collectively referred to as a fluid guide flow path. Specifically, respective reaction gas flow paths 22 are formed between the separators 6 and 7 and the gas diffusion layers 4 and 5. A cooling medium flow path 21 is formed between the partition plates 6 and 7 separating adjacent individual units. Use antifreeze agents such as water and glycol, air, etc. as the cooling medium. As shown in FIG. 1, the fuel gas (anode gas) is supplied from the reaction gas flow path 22 of the anode side separator 6. The fuel gas may be, for example, hydrogen gas, methane gas, or the like. An oxidizing gas (cathode gas) is supplied from the reaction gas flow path 22 of the cathode side separator 7. The oxidizing gas may be, for example, a gas containing oxygen such as oxygen and air.
对燃料电池中的冷却介质的循环系统进行说明。经由水泵和配管，将利用散热器冷却后的冷却介质提供至燃料电池堆。将提供至燃料电池堆的冷却介质经由冷却介质供给用歧管分配到各单个单元，并对各单个单元进行冷却。对各单个单元进行冷却后的冷却介质经由冷却介质排出用歧管收集，经由配管在散热器中进行循环。The circulation system of the cooling medium in the fuel cell will be described. The cooling medium cooled by the radiator is supplied to the fuel cell stack via a water pump and piping. The cooling medium supplied to the fuel cell stack is distributed to the individual units via the cooling medium supply manifold, and the individual units are cooled. The cooling medium after cooling each individual unit is collected through the cooling medium discharge manifold, and circulates in the radiator through the pipe.
对燃料气体的循环系统进行说明。从储存高压氢气的氢气罐经由截止阀、调节器、配管将燃料气体提供到燃料电池堆。将提供到燃料电池堆的燃料气体经由燃料气体供给用歧管分配到各单个单元，并用于各单个单元的发电。在各单个单元中未使用的燃料气体经由燃料气体排出用歧管被收集，并经由排出配管排出到燃料电池堆的外部。The fuel gas circulation system will be described. The fuel gas is supplied to the fuel cell stack from a hydrogen tank storing high-pressure hydrogen gas via a shut-off valve, regulator, and piping. The fuel gas supplied to the fuel cell stack is distributed to each individual unit via a fuel gas supply manifold, and is used for power generation of each individual unit. The unused fuel gas in each individual unit is collected through a fuel gas discharge manifold, and is discharged to the outside of the fuel cell stack through a discharge pipe.
对氧化气体的循环系统进行说明。经由气泵和配管将氧化气体提供到燃料电池堆。将提供到燃料电池堆的氧化气体经由氧化气体供给用歧管分配到各单个单元，并用于各单个单元的发电。在各单个单元中未使用的氧化气体经由氧化气体排出用歧管收集，并经由排出配管排出到燃料电池堆的外部。另外，在本说明书中，燃料气体和氧化气体也被称为反应气体。The circulation system of the oxidizing gas will be described. The oxidizing gas is supplied to the fuel cell stack via an air pump and piping. The oxidizing gas supplied to the fuel cell stack is distributed to the individual units via the oxidizing gas supply manifold, and used for power generation of the individual units. The unused oxidizing gas in each individual unit is collected through the oxidizing gas discharge manifold, and is discharged to the outside of the fuel cell stack through the discharge pipe. In addition, in this specification, fuel gas and oxidizing gas are also referred to as reaction gas.
(隔板的结构)(Structure of partition)
本发明的隔板6、7大致如图2A所示，由矩形的柔性膜材构成，在长边方向的一个边缘形成有沿着宽度方向大致为矩形的流体的供给口31，在另一个边缘形成有沿着宽度方向大致为矩形的流体的排出口32，从供给口31向排出口32(即沿着长边方向)从多个肋部11形成有流体引导流路。该隔板6、7中，从供给口31提供的流体沿着流体引导流路流动，未用于发电的流体通过排出口32排 出。这里的流体分别是氧化气体、燃料气体、冷却介质。The separators 6 and 7 of the present invention are roughly as shown in FIG. 2A and are composed of a rectangular flexible film material. One edge in the longitudinal direction is formed with a fluid supply port 31 that is substantially rectangular in the width direction. A fluid discharge port 32 that is substantially rectangular in the width direction is formed, and a fluid guide flow path is formed from the plurality of ribs 11 from the supply port 31 to the discharge port 32 (that is, along the longitudinal direction). In the separators 6 and 7, the fluid supplied from the supply port 31 flows along the fluid guide flow path, and the fluid not used for power generation is discharged through the discharge port 32. The fluids here are oxidizing gas, fuel gas, and cooling medium.
本发明着眼于将冷却介质或反应气体等流体提供到MEA的隔板基材的中央部的活性区域(发电区域)的结构。在图2A中，示出冷却介质流路21侧的隔板，用虚线包围的区域相当于该活性区域。在本发明的隔板的活性区域的外缘形成有内部歧管的开口孔33。并且为了阻止氧化气体、燃料气体、冷却介质的泄漏，在外周设置所需的密封材料20。图2B是沿着图2A隔板的S-S’线的剖视图。The present invention focuses on a structure in which a fluid such as a cooling medium or a reaction gas is supplied to the active area (power generation area) of the central part of the separator substrate of the MEA. In FIG. 2A, the partition on the side of the cooling medium flow path 21 is shown, and the area enclosed by the broken line corresponds to the active area. The opening hole 33 of the internal manifold is formed on the outer edge of the active area of the separator of the present invention. In order to prevent the leakage of oxidizing gas, fuel gas, and cooling medium, a required sealing material 20 is provided on the outer periphery. Fig. 2B is a cross-sectional view taken along the line S-S' of the separator of Fig. 2A.
本发明的隔板6、7是使用由高导电性/热传导性柔性膜材构成的两个个隔板基材100来制作的。对于该隔板基材100来说，通过使用专用的装置附着(例如涂布、印刷、点胶、喷射、转印等)包含导电性材料、粘结树脂、溶剂、其他添加物、导电性强化材料及其他附着材料的前驱体(附着前的状态、硬化反应前的状态)，从而在隔板基材100表面形成流体引导流路。The separators 6 and 7 of the present invention are manufactured using two separator base materials 100 composed of a highly conductive/thermally conductive flexible film material. The separator substrate 100 is attached by using a dedicated device (for example, coating, printing, dispensing, spraying, transfer, etc.), including conductive materials, bonding resins, solvents, other additives, and conductivity enhancement The precursor of the material and other adhesion materials (the state before adhesion and the state before the curing reaction) forms a fluid guiding flow path on the surface of the separator substrate 100.
即，本发明的隔板是由两个隔板基材100以及形成在该两个隔板基材100间的冷却介质流路21构成的高分子型燃料电池的构成部件。此外，在如上所述的隔板的外侧表面(设置有冷却介质流路21的面的相反面)分别形成阳极和阴极的反应气体流路22，从而形成阳极侧隔板6和阴极侧隔板7。That is, the separator of the present invention is a component of a polymer fuel cell composed of two separator base materials 100 and a cooling medium flow path 21 formed between the two separator base materials 100. In addition, the anode and cathode reaction gas flow paths 22 are formed on the outer surface of the separator as described above (the surface opposite to the surface where the cooling medium flow path 21 is provided), thereby forming the anode side separator 6 and the cathode side separator. 7.
用图2B对本发明的隔板的基本结构进行说明。如图2B所示，本发明的隔板的主要组件在后述的所有的实施方式1～3中共用。The basic structure of the separator of the present invention will be described with reference to FIG. 2B. As shown in FIG. 2B, the main components of the separator of the present invention are shared in all the embodiments 1 to 3 described later.
(1)隔板基材100(1) Separator base material 100
(2)表面处理层和/或表面改质层105(2) Surface treatment layer and/or surface modification layer 105
(3)强化层(任意)106(3) Strengthening layer (optional) 106
(4)冷却介质流路21(4) Cooling medium flow path 21
(5)反应气体流路22(燃料气体、氧化气体)(5) Reactive gas flow path 22 (fuel gas, oxidizing gas)
总体来说，优良的隔板必须具有气密性，从而可以防止电池内各种流体间的扩散混合，并且为了具有优良的集电体而必须具有足够的导电性。若隔板较厚则会引起内部电阻增大，因此隔板不能过厚。例如，隔板的厚度可以是10～1,000μm。为了将反应热释放到外部，隔板还需要具有热传导性/散热性。除此以外，隔板还需要具备耐腐蚀性、刚性、能以低成本的卷对卷方式(将流路图案附着在卷成圆筒状的基材后，再次卷成圆筒状，使其在装置之间连续地流动的量产方法)生产。基于上述思想构建本发明的隔板。In general, a good separator must have airtightness, so as to prevent the diffusion and mixing of various fluids in the battery, and must have sufficient conductivity in order to have a good current collector. If the separator is thick, the internal resistance will increase, so the separator cannot be too thick. For example, the thickness of the separator may be 10 to 1,000 μm. In order to release the reaction heat to the outside, the separator also needs to have thermal conductivity/dissipation properties. In addition, the separator also needs to have corrosion resistance, rigidity, and a low-cost roll-to-roll method (after attaching the flow path pattern to the substrate rolled into a cylindrical shape, it is rolled into a cylindrical shape again to make it Mass production method that continuously flows between devices) production. The separator of the present invention is constructed based on the above-mentioned idea.
另外，在本说明书中，“附着”是指将具有粘度的附着材料(糊料、浆料、墨水)作为三维构造体覆盖在表面。“涂布”是使较薄的膜覆盖在表面。In addition, in this specification, "adhesion" means that an adhesion material (paste, slurry, ink) having a viscosity is covered on the surface as a three-dimensional structure. "Coating" is to cover the surface with a thinner film.
下面，参照图2A至图6对于各组件的结构进行描述。Hereinafter, the structure of each component will be described with reference to FIGS. 2A to 6.
(1)基材(base material)(1) Base material
本发明中的基材是指成为附着有流体引导流路的基底的构件，相当于该基材的是形成隔板6、7的隔板基材100以及作为气体扩散层4、5的气体扩散层基材。本发明主要着眼于使肋部结构体附着的隔板基材100进行说明。在将气体扩散层4、5作为附着肋部结构体的表面的情况下，该气体扩散层4、5的表面成为附着面。The substrate in the present invention refers to a member that becomes the base to which the fluid guide flow path is attached. The substrate is equivalent to the separator substrate 100 forming the separators 6, 7 and the gas diffusion layer 4, 5 as the gas diffusion layer. Layer substrate. The present invention will be described mainly focusing on the separator substrate 100 to which the rib structure is attached. When the gas diffusion layers 4 and 5 are used as the surfaces of the adhesion rib structure, the surfaces of the gas diffusion layers 4 and 5 become the adhesion surfaces.
图2C所示的隔板基材100的主要作用是使隔板具有导电性、热传导性，能应对卷对卷方式的量产而使总成本较低的意义上的柔软的结构体(柔性膜材)，以及用于在其表面形成流体引导流路的基板。本发明中，使用能实现高导电性、高热传导性、高输出功率体积密度、高输出功率重量密度的片状的结构体作为隔板基材100。期望隔板基材100具有导电性、热传导性，能以较低的材料成本生产，能适用卷对卷方式，能实现厚度变薄、轻量化。The main function of the separator substrate 100 shown in FIG. 2C is to make the separator have electrical conductivity and thermal conductivity, which can cope with the mass production of the roll-to-roll method and make the total cost of the flexible structure (flexible film) low. Material), and a substrate for forming a fluid guiding flow path on its surface. In the present invention, a sheet-like structure capable of achieving high electrical conductivity, high thermal conductivity, high output volume density, and high output weight density is used as the separator substrate 100. It is desirable that the separator substrate 100 has electrical conductivity and thermal conductivity, can be produced at a lower material cost, can be applied to a roll-to-roll method, and can achieve thinner thickness and lighter weight.
隔板基材100是包括至少一种导电性材料以及至少一种树脂组成物。该导电性材料可以是导电性碳材料。隔板基材100还包括至少一种导电性强化材料。该导电性强化材料可以是导电性碳素强化材料。The separator substrate 100 includes at least one conductive material and at least one resin composition. The conductive material may be a conductive carbon material. The separator substrate 100 further includes at least one conductive reinforcing material. The conductive reinforcing material may be a conductive carbon reinforcing material.
隔板基材100是由导电性碳材料、树脂组成物以及导电性碳素强化材料构成的高导电性碳复合柔性膜材。作为导电性碳材料，混合有石墨粉、碳粉、碳黑等。作为树脂组成物，混合有热塑性树脂(聚乙烯，聚丙烯等)和热固性树脂(酚醛树脂、环氧树脂等)。作为导电性碳强化材料，混合有碳纤维、碳纳米管、石墨烯等。将这些材料形成为一体、薄而柔软的高导电性碳复合柔性膜材。该高导电性碳复合柔性膜材是将导电性材料、树脂、以及强化材料组合后得到的材料。隔板基材100一般的制造工艺是层叠上述材料，用具有弹性的膜覆盖层叠体，通过加压/加热使其硬化来完成。The separator substrate 100 is a highly conductive carbon composite flexible film material composed of a conductive carbon material, a resin composition, and a conductive carbon reinforcement material. As the conductive carbon material, graphite powder, carbon powder, carbon black, etc. are mixed. As the resin composition, a thermoplastic resin (polyethylene, polypropylene, etc.) and a thermosetting resin (phenol resin, epoxy resin, etc.) are mixed. As a conductive carbon reinforcement material, carbon fiber, carbon nanotube, graphene, etc. are mixed. These materials are formed into a one-piece, thin and flexible high-conductivity carbon composite flexible membrane material. The highly conductive carbon composite flexible film material is a material obtained by combining conductive materials, resins, and reinforcing materials. The general manufacturing process of the separator substrate 100 is to laminate the above-mentioned materials, cover the laminate with an elastic film, and harden it by applying pressure/heating.
作为一个示例，隔板基材100的特性是薄片状，具有平坦的主面。为了提高隔板基材100的刚性、导电性、热传导性以及不透气性，在隔板基材100成型时加入强化树脂、细石墨纤维和/或碳纳米管和/或石墨烯等导电性强化材料。 此外，为了获得兼容性更高、接触电阻以及界面热传导良好的隔板基材100，使细石墨纤维和/或碳纳米管等导电性强化材料在隔板基材100的延伸面以垂直方向或倾斜贯通方向取向排列。As an example, the characteristic of the separator substrate 100 is a sheet-like shape with a flat main surface. In order to improve the rigidity, conductivity, thermal conductivity, and gas impermeability of the separator substrate 100, conductive reinforcement such as reinforced resin, fine graphite fibers and/or carbon nanotubes and/or graphene is added during the molding of the separator substrate 100 material. In addition, in order to obtain a separator substrate 100 with higher compatibility, good contact resistance, and good interface heat conduction, conductive reinforcing materials such as fine graphite fibers and/or carbon nanotubes are arranged on the extended surface of the separator substrate 100 in a vertical direction or Aligned in an oblique through direction.
此外，作为本发明中能使用的隔板基材100，只要其厚度薄、重量轻，能提供冷却介质、反应气体不相混合的水密性和/或气密性，是导电率和热传导率较高、能耐受劣化等化学变化的材料，是能适用于卷对卷方式量产的厚度的柔性膜材，则不限于上述高导电性碳复合柔性膜材，也可以广泛使用现成产品等已知物品。In addition, as the separator substrate 100 that can be used in the present invention, as long as it has a thin thickness and a light weight, it can provide water tightness and/or air tightness in which the cooling medium and reaction gas are not mixed, and the conductivity and thermal conductivity are relatively high. The material is high and can withstand chemical changes such as degradation. It is a flexible film with a thickness suitable for roll-to-roll mass production. It is not limited to the above-mentioned high-conductivity carbon composite flexible film, and ready-made products can also be widely used. Know items.
为了实现隔板的薄板化、轻量化，隔板基材100的厚度优选为10～100μm的范围，更优选为10～50μm的范围。In order to achieve thinning and weight reduction of the separator, the thickness of the separator base 100 is preferably in the range of 10 to 100 μm, and more preferably in the range of 10 to 50 μm.
隔板的导电率通过隔板基材100所具有的导电性和构成流体引导流路的功能材料所具有的导电性来提高。例如，隔板基材100和流体引导流路的功能材料中所含有的碳纤维是导电或导热较好的材料。The electrical conductivity of the separator is improved by the electrical conductivity of the separator base 100 and the electrical conductivity of the functional material constituting the fluid guiding flow path. For example, the carbon fiber contained in the separator substrate 100 and the functional material of the fluid guiding flow path is a material with good electrical or thermal conductivity.
关于隔板基材100的热传导，例如，可以通过使作为导热较好的材料的石墨取向来制作柔性膜材，该柔性膜材具有使由于发电而产生的热高效地释放的散热功能，并且难以引起劣化，也可附加地增加热传导性。隔板基材100的热传导率至少约为700W/mk。Regarding the heat conduction of the separator substrate 100, for example, a flexible film material can be produced by orienting graphite, which is a material with good thermal conductivity, which has a heat dissipation function to efficiently release heat generated by power generation, and is difficult to Deterioration is caused, and thermal conductivity can be additionally increased. The thermal conductivity of the separator substrate 100 is at least about 700 W/mk.
(2)表面处理层、表面改质层(2) Surface treatment layer, surface modification layer
表面处理层和/或表面改质层105是对隔板基材100进行被膜，使基材表面接触电阻降低，提高基材与后述的强化层106或流体引导流路的接合性和密接性的层。在气体扩散层基材不设置表面处理层和/或表面改质层105。为了降低接触电阻值，提高与隔板基材的接合性和密接性，需要施加特殊的表面处理来提高兼容性。若界面接合性和密接性不够，则随着长时间经过会逐渐失去导电性，电阻变高，发电性能变差。为了获得足够的接合性和密接性，在从基材表面去除异物和污染等污垢的同时，需要进行改质或改性以提高基材表面的附着性和亲和性。也就是说进行表面预处理，以提高基材表面的润湿性。作为设置表面处理层105的方法，可以包括例如旋涂、狭缝涂布、喷涂、浸涂、棒涂等各种涂装方法，各种气体中的溅射，化学气相沉积和物理气相沉积等气相沉积方法，以及其他适当的方法等。作为提高表面附着性的表面改质处理的方法，可以包 括例如利用酸等化学药品进行的蚀刻、等离子处理、电晕放电处理、框架处理、臭氧处理、紫外线处理、以及其他适当的处理等。The surface treatment layer and/or the surface modification layer 105 coat the separator substrate 100 to reduce the surface contact resistance of the substrate and improve the adhesion and adhesion between the substrate and the reinforcing layer 106 or the fluid guiding flow path described later.的层。 The layer. The surface treatment layer and/or the surface modification layer 105 are not provided on the gas diffusion layer base material. In order to reduce the contact resistance value and improve the adhesion and adhesion with the separator substrate, it is necessary to apply a special surface treatment to improve compatibility. If the interface adhesion and adhesion are insufficient, the electrical conductivity will gradually be lost over a long period of time, the electrical resistance will increase, and the power generation performance will deteriorate. In order to obtain sufficient adhesion and adhesion, it is necessary to modify or modify the surface of the substrate while removing foreign matter and contaminants from the surface of the substrate to improve the adhesion and affinity of the substrate surface. In other words, surface pretreatment is performed to improve the wettability of the substrate surface. As a method of setting the surface treatment layer 105, various coating methods such as spin coating, slit coating, spray coating, dip coating, bar coating, etc., sputtering in various gases, chemical vapor deposition, and physical vapor deposition can be included. Vapor deposition method, and other appropriate methods, etc. As a method of surface modification treatment to improve surface adhesion, for example, etching with chemicals such as acid, plasma treatment, corona discharge treatment, frame treatment, ozone treatment, ultraviolet treatment, and other appropriate treatments can be included.
在图2C中示出形成有表面处理层和/或表面改质层105的隔板基材100的典型示例。釆用将隔板基材100浸渍在处理液中进行表面改质的手法，其使用的处理液需优选为不侵入基材的处理液。或者，在处理之后通过使碳系涂层材料蒸镀在隔板基材100表面上，从而能获得表面处理层和/或表面改质层105。例如，表面处理层105的厚度可以是1～1,000nm。表面改质层105的厚度可以是0.1～1,000nm。另外，为了提高隔板基材100的水密性/气密性，优选为将表面处理层和/或表面改质层105至少设置在被后述的流体引导流路附着的隔板基材100的单面上。A typical example of the separator substrate 100 formed with the surface treatment layer and/or the surface modification layer 105 is shown in FIG. 2C. The method of immersing the separator substrate 100 in the treatment liquid for surface modification is adopted, and the treatment liquid used should preferably be a treatment liquid that does not invade the substrate. Alternatively, by vapor-depositing the carbon-based coating material on the surface of the separator substrate 100 after the treatment, the surface treatment layer and/or the surface modification layer 105 can be obtained. For example, the thickness of the surface treatment layer 105 may be 1 to 1,000 nm. The thickness of the surface modification layer 105 may be 0.1 to 1,000 nm. In addition, in order to improve the water-tightness/air-tightness of the separator substrate 100, it is preferable to provide the surface treatment layer and/or the surface modification layer 105 at least on the separator substrate 100 adhered to the fluid guide flow path described later. Single side.
其理由是：固体高分子型燃料电池用的隔板具有包含水蒸气的反应气体的流路，在高温、酸性条件下使用，维持表面处理层和/或表面改质层105的耐腐蚀性是非常重要的。The reason is that the separator for the polymer electrolyte fuel cell has a flow path of the reaction gas containing water vapor, and is used under high temperature and acidic conditions to maintain the corrosion resistance of the surface treatment layer and/or the surface modification layer 105. very important.
当然，该表面处理层和/或表面改质层105作为具有导电性的导电层，对隔板基材100的双面进行覆盖也是重要的。Of course, the surface treatment layer and/or the surface modification layer 105 serves as a conductive layer with conductivity, and it is also important to cover both sides of the separator substrate 100.
可以设置使表面处理层105的碳组分的密度从隔板基材100侧向强化层106侧方向变高这样的倾斜功能结构。由此，强化层106的内部应力降低。由于内部应力降低，能防止隔板基材100或其他材料层(强化层106等)的弯曲，能阻止裂纹等发生，界面剥离也难以产生。It is possible to provide an inclined functional structure that increases the density of the carbon component of the surface treatment layer 105 from the separator base material 100 side toward the reinforcement layer 106 side. As a result, the internal stress of the reinforcement layer 106 is reduced. Due to the reduction in internal stress, the separator substrate 100 or other material layers (reinforcing layer 106, etc.) can be prevented from bending, cracks, etc., can be prevented from occurring, and interface peeling is also difficult to occur.
(3)强化层(reinforced layer)(3) Reinforced layer
强化层106是能在隔板基材100实施表面处理和/或表面改质处理的表面处理层和/或表面改质层105上进行被膜的层。在气体扩散层基材上不设置强化层106。由于隔板基材100是非常薄的材料，因此期望对隔板基材100进行强化。从而，如图2C所示，建议在上述的表面处理层和/或表面改质层105上设置强化层106。例如，强化层106的厚度可以是1～50μm。出于赋予水密性的目的，可以在面向冷却介质流路21的一侧设置强化层106。为了提高与肋部11结构体界面的接合性和密接性，在强化层106上涂疏水涂层，将表示浸润性的接触角设为中等程度，从而能对三维形状的肋部11结构体进行造型。另外，作为强化层106的材料，可以是与后述的冷却介质流路21的附着材料以及反应气体流路22 的附着材料同质的材料，可以与它们的混合比例不同，也可以是异质的材料。此外，可以在完成表面处理/表面改质的隔板基材100的活性区域的整个面上设置强化层106，可以局部地设置强化层106，也可以不设置强化层106。作为强化层106的材料，只要是具有导电性和热传导性、能在表面处理层和/或表面改质层105上进行被膜、表面处理层和/或表面改质层105与各种流体引导流路的附着材料的接合性和密接性良好、能有助于提高隔板基材100的刚性的材料，则不特别限定。例如，也可以使用导电性聚合物中分散了导电性纳米颗粒的分散材料、以及将通过相分离形成的碳作为主要成分的纳米结构材料。The reinforcement layer 106 is a layer that can be coated on the surface treatment layer and/or the surface modification layer 105 to which the separator substrate 100 is subjected to surface treatment and/or surface modification treatment. The reinforcing layer 106 is not provided on the gas diffusion layer base material. Since the separator substrate 100 is a very thin material, it is desirable to strengthen the separator substrate 100. Therefore, as shown in FIG. 2C, it is recommended to provide a strengthening layer 106 on the above-mentioned surface treatment layer and/or surface modification layer 105. For example, the thickness of the reinforcement layer 106 may be 1-50 μm. For the purpose of imparting water tightness, a reinforcing layer 106 may be provided on the side facing the cooling medium flow path 21. In order to improve the adhesion and adhesion of the interface with the rib 11 structure, a hydrophobic coating is applied to the reinforcement layer 106, and the contact angle indicating the wettability is set to a medium level, so that the three-dimensional shape of the rib 11 structure can be processed. modeling. In addition, the material of the reinforcement layer 106 may be the same material as the adhesion material of the cooling medium flow path 21 and the adhesion material of the reaction gas flow path 22 described later, may be different from their mixing ratio, or may be a heterogeneous material. s material. In addition, the reinforcement layer 106 may be provided on the entire surface of the active area of the separator substrate 100 after the surface treatment/surface modification has been completed, the reinforcement layer 106 may be provided locally, or the reinforcement layer 106 may not be provided. As the material of the strengthening layer 106, as long as it has conductivity and thermal conductivity, can be coated on the surface treatment layer and/or the surface modification layer 105, the surface treatment layer and/or the surface modification layer 105 and various fluids guide flow The adhesive material of the road has good adhesion and adhesiveness, and can contribute to the improvement of the rigidity of the separator substrate 100, and it is not particularly limited. For example, it is also possible to use a dispersion material in which conductive nanoparticles are dispersed in a conductive polymer, and a nanostructure material in which carbon formed by phase separation is a main component.
(4)冷却介质流路(4) Cooling medium flow path
本发明所涉及的冷却介质流路21是位于两个隔板基材100(第一隔板基材101和第二隔板基材102)之间的流路。在两个隔板基材100中的至少一个隔板基材100表面上形成冷却介质流路21。例如，在第一隔板基材101上形成冷却介质流路21，使第二隔板基材102和第一隔板基材102贴合。在该贴合的第二隔板基材102上未设置冷却介质流路21。通过将两个隔板基材贴合，从而在它们的中间位置完成冷却介质流路21。或者，也可以在第一隔板基材101和第二隔板基材102上交替设置冷却介质流路21的肋部11并啮合。包括冷却介质流路21和气体引导流路22在内的流体引导流路的高度可以是1～500μm。The cooling medium flow path 21 according to the present invention is a flow path located between the two separator substrates 100 (the first separator substrate 101 and the second separator substrate 102). A cooling medium flow path 21 is formed on the surface of at least one of the two separator substrates 100. For example, the cooling medium flow path 21 is formed in the first separator substrate 101, and the second separator substrate 102 and the first separator substrate 102 are bonded together. The cooling medium flow path 21 is not provided in the bonded second separator substrate 102. By bonding the two separator base materials together, the cooling medium flow path 21 is completed in the middle of the two separator substrates. Alternatively, the ribs 11 of the cooling medium flow path 21 may be alternately provided on the first separator substrate 101 and the second separator substrate 102 and meshed. The height of the fluid guide flow path including the cooling medium flow path 21 and the gas guide flow path 22 may be 1 to 500 μm.
在图6中示出了冷却介质流路21的平面图案的几个示例。冷却介质流路21的形状并不特别限定，可以在主旨的范围内进行各种改变来设计，例如蛇形、直线形、锯齿形、条纹形、凹坑形等。Several examples of the planar pattern of the cooling medium flow path 21 are shown in FIG. 6. The shape of the cooling medium flow path 21 is not particularly limited, and can be designed with various changes within the scope of the subject matter, such as a serpentine shape, a linear shape, a zigzag shape, a stripe shape, a pit shape, and the like.
对构成冷却介质流路21的多个肋部11(流体引导流路的突起部)进行造型的功能材料(以下称为附着材料)并不特别限定。可以使用诸如涂布、印刷、点胶、喷射、转印等附着方法，并且可以使附着材料的前驱体(糊料、浆料或墨水)附着、加热/干燥，只要结果能获得具有覆盖在隔板基材100上的作用的附着材料即可。另外，在本说明书中，将糊料、浆料、墨水等的加热/干燥前的材料称为“附着材料的前驱体”，将覆盖在隔板基材100上的加热/干燥后的材料称为“附着材料”。作为这种附着材料，有致密性碳基材料和/或多孔碳基材料。The functional material (hereinafter referred to as an adhesion material) that shapes the plurality of ribs 11 (protrusions of the fluid guide flow path) constituting the cooling medium flow path 21 is not particularly limited. Adhesion methods such as coating, printing, dispensing, spraying, transfer, etc. can be used, and the precursor of the adhering material (paste, slurry, or ink) can be adhered, heated/dried, as long as the result can be obtained What is necessary is just an adhesion material which functions on the board base material 100. In addition, in this specification, the material before heating/drying of paste, slurry, ink, etc. is referred to as "precursor of adhesion material", and the heated/dried material covering the separator substrate 100 is referred to as It is the "attachment material". As such attachment materials, there are dense carbon-based materials and/or porous carbon-based materials.
构成冷却介质流路21的肋部11是高导电性附着材料。附着材料需要具有在 燃料电池的动作温度下、或热冲压等压接温度下不变形这样水平的耐热性。通过包含于附着材料的细碳纤维与导电树脂缠绕，能获得更高导电性、高机械强度、高耐热强度的肋部11。由此，作为附着材料，只要是导电性优异同时热传导性良好，难以劣化，能赋予刚性/强化性的材料，则不作限定。The rib 11 constituting the cooling medium flow path 21 is a highly conductive adhesive material. The adhesive material needs to have a level of heat resistance that does not deform at the operating temperature of the fuel cell or at the pressure bonding temperature such as hot stamping. By winding the fine carbon fiber contained in the adhesive material with the conductive resin, the rib 11 with higher conductivity, high mechanical strength, and high heat resistance strength can be obtained. Therefore, as the adhesion material, there is no limitation as long as it has excellent electrical conductivity and good thermal conductivity, is hard to be deteriorated, and can impart rigidity/reinforcement.
(5)反应气体流路(5) Reactive gas flow path
如上所述的隔板至少在单个隔板基材100的一个面上设置冷却介质流路21。换言之，对于在隔板基材100的内侧安装有冷却介质流路21的隔板，在其外侧的面上，形成有作为反应气体流路22的通道(即，燃料气体流路和氧化气体流路)。反应气体流路22可以设置在贴合的两个隔板基材100的单面，也可以将反应气体流路22的局部或全部设置在气体扩散层基材表面。The separator as described above is provided with a cooling medium flow path 21 on at least one surface of a single separator substrate 100. In other words, for the separator with the cooling medium flow path 21 mounted on the inner side of the separator base 100, the channel as the reaction gas flow path 22 (that is, the fuel gas flow path and the oxidizing gas flow path) is formed on the outer surface of the separator. road). The reaction gas flow path 22 may be provided on one side of the two bonded separator substrates 100, or part or all of the reaction gas flow path 22 may be provided on the surface of the gas diffusion layer substrate.
通过以适当的组成比均等地将反应气体提供到两个反应气体流路22，除了能提高输出功率面密度以外，还能提高燃料电池本身的效率。本发明中，在上述较薄的基材面上，附着的流体引导流路肋部的高度是由反应气体等的压力损耗要求等决定的，因此能使单体隔板厚度变薄，能使单元间距变窄。由此，能提高燃料电池的输出功率体积密度。例如，流体引导流路的高度可以是1～500μm。By uniformly supplying the reaction gas to the two reaction gas flow paths 22 with an appropriate composition ratio, in addition to increasing the output power areal density, the efficiency of the fuel cell itself can also be improved. In the present invention, the height of the ribs of the fluid guide flow path attached to the thinner substrate surface is determined by the pressure loss requirements of the reactant gas, etc., so the thickness of the cell separator can be made thinner. The cell pitch becomes narrower. As a result, the output volume density of the fuel cell can be improved. For example, the height of the fluid guiding flow path may be 1 to 500 μm.
参考图1，为了使本发明的隔板6起到阳极侧的作用，在与膜电极接合体MEA的阳极侧气体扩散层4相对的一个隔板面上形成燃料气体通过的反应气体流路22，另一个平坦的面与冷却介质流路21抵接。为了使本发明的隔板7起到阴极侧的作用，在与膜电极接合体MEA的阴极侧气体扩散层5相对的一个隔板面上形成含氧的氧化气体通过的反应气体流路22，另一个平坦的面与冷却介质流路21抵接。各个反应气体流路可以设置在贴合后的隔板基材100的任意外侧。这样接收反应气体的供给，使本发明的燃料电池进行发电。1, in order for the separator 6 of the present invention to function as the anode side, a reaction gas flow path 22 through which fuel gas passes is formed on a separator surface opposite to the anode gas diffusion layer 4 of the membrane electrode assembly MEA. , The other flat surface is in contact with the cooling medium flow path 21. In order for the separator 7 of the present invention to function on the cathode side, a reaction gas flow path 22 through which oxygen-containing oxidizing gas passes is formed on one of the separator surfaces facing the cathode side gas diffusion layer 5 of the membrane electrode assembly MEA. The other flat surface is in contact with the cooling medium flow path 21. Each reactive gas flow path may be provided on any outside of the bonded separator substrate 100. In this way, the supply of reactant gas is received, and the fuel cell of the present invention generates power.
在附着各个反应气体流路22之前，两个隔板基材100间设置有冷却介质流路21并贴合的隔板可以说是燃料电池的阳极与阴极中共用的构件。在附着了燃料气体流路和氧化气体流路时，开始识别出阳极侧和阴极侧。Before each reaction gas flow path 22 is attached, the separator in which the cooling medium flow path 21 is provided between the two separator substrates 100 and bonded together can be said to be a common member for the anode and cathode of the fuel cell. When the fuel gas flow path and the oxidizing gas flow path are attached, the anode side and the cathode side are recognized.
此外，各个反应气体流路22的平面图案并不特别限定，可以在其主旨的范围内进行各种改变来分别设计，例如蛇形、蛇形的旋转形状、直线形、凹坑形状或其他形状等。In addition, the planar pattern of each reaction gas flow path 22 is not particularly limited, and various changes can be made within the scope of its theme to design separately, such as a serpentine shape, a serpentine rotation shape, a linear shape, a pit shape, or other shapes. Wait.
如上所述，对构成反应气体流路22的多个肋部12(流体引导流路的突起部)进行造型的附着材料并不特别限定。与形成冷却介质流路21时相同，可以使用诸如涂布、印刷、点胶、喷射、转印等附着方法，并且可以使附着材料的前驱体(糊料、浆料或墨水)附着、加热/干燥，只要结果是能获得具有覆盖在隔板基材100上的作用的附着材料即可。作为这种附着材料，有致密的碳基材料和/或多孔碳基材料。使这种附着材料附着在隔板表面和/或面向隔板的气体扩散层表面。As described above, the adhesion material that shapes the plurality of ribs 12 (protrusions of the fluid guide flow path) constituting the reaction gas flow path 22 is not particularly limited. As with the formation of the cooling medium flow path 21, adhesion methods such as coating, printing, dispensing, jetting, and transfer can be used, and the precursor (paste, slurry, or ink) of the adhesion material can be adhered and heated/ Drying, as long as the result is that an adhesive material having a function of covering the separator substrate 100 can be obtained. As such attachment materials, there are dense carbon-based materials and/or porous carbon-based materials. The attachment material is attached to the surface of the separator and/or the surface of the gas diffusion layer facing the separator.
与冷却介质流路21的肋部11相同，反应气体流路22的肋部12是高导电性附着材料。由此，作为反应气体流路22的附着材料，期望是导电性优异同时热传导性良好，难以劣化，能赋予刚性/强化性的材料。Like the rib 11 of the cooling medium flow path 21, the rib 12 of the reaction gas flow path 22 is a highly conductive adhesive material. Therefore, as the adhesion material of the reaction gas flow path 22, it is desirable to be a material that has excellent electrical conductivity and good thermal conductivity, is hard to be deteriorated, and can impart rigidity and strengthening properties.
能使用与用于冷却介质流路21的附着材料相同的材料作为能用于各个反应气体流路22的附着材料。或者，能根据各流体引导流路各自要求的特性，使其附着材料的成分部分不同。各个反应气体流路可以在阳极和阴极使用同质的附着材料，也可以使用异质的附着材料。The same material as the adhesion material used for the cooling medium flow path 21 can be used as the adhesion material that can be used for each reaction gas flow path 22. Alternatively, the composition of the adhesion material can be partially different according to the characteristics required for each fluid guide flow path. Each reaction gas flow path may use the same adhesion material for the anode and the cathode, or a heterogeneous adhesion material.
例如，在使用多孔碳基材料作为反应气体流路22的附着材料的情况下，由于其存在空隙，因此能高效地从冷却对象带走热量。这是由于存在空隙能确保通气性，因此在阴极侧存在的丰富的水等液体进行汽化时，从周围带走汽化热，具有冷却的效果。这种多孔碳基材料优选的用于作为氧化气体流路的附着材料。For example, in the case where a porous carbon-based material is used as the adhesion material of the reaction gas flow path 22, since there are voids, heat can be efficiently taken away from the cooling target. This is because the existence of voids can ensure air permeability, so when the abundant liquid such as water existing on the cathode side vaporizes, the heat of vaporization is taken away from the surroundings and has a cooling effect. Such a porous carbon-based material is preferably used as an attachment material for an oxidizing gas flow path.
另外，本发明提到的“接合性/密接性”这个词的含义是，在隔板基材100的表面与表面处理层和/或表面改质层105之间、在表面处理层和/或表面改质层105与强化层106之间、在覆盖隔板基材100的表面处理层和/或表面改质层105与冷却介质流路的肋部11底部之间、在覆盖隔板基材100的表面处理层和/或表面改质层105与反应气体流路的肋部12底部之间、在强化层106与冷却介质流路的肋部11底部之间、在强化层106与反应气体流路的肋部12底部之间、在强化部106A与表面处理层和/或表面改质层105之间以及其他各相邻层之间发生界面剥离和/或界面附近剥离所需要的能量。In addition, the term "adhesion/adhesion" mentioned in the present invention means between the surface of the separator substrate 100 and the surface treatment layer and/or the surface modification layer 105, between the surface treatment layer and/or Between the surface modification layer 105 and the reinforcing layer 106, between the surface treatment layer covering the separator substrate 100 and/or between the surface modification layer 105 and the bottom of the rib 11 of the cooling medium flow path, and between the covering separator substrate 100 100 between the surface treatment layer and/or surface modification layer 105 and the bottom of the rib 12 of the reaction gas flow path, between the reinforcing layer 106 and the bottom of the rib 11 of the cooling medium flow path, between the reinforcing layer 106 and the bottom of the rib 11 The energy required for interfacial peeling and/or near-interface peeling between the bottoms of the ribs 12 of the flow path, between the reinforced portion 106A and the surface treatment layer and/or the surface modification layer 105, and between other adjacent layers.
如上所述，对构成(1)～(5)的各材料并不特别限定，掌握各组件所要求的功能，根据期望选择最适合的材料，使这些组成材料的特性被适当地应用 即可。此外，本发明的隔板的制造方法不做特别限制，只要考虑到所希望的隔板基材100的结构、材质、流体引导流路的材料、其他燃料电池构成部件的产品形状等，选择适当优选的条件即可。As described above, the materials constituting (1) to (5) are not particularly limited, and the functions required for each component are grasped, the most suitable materials are selected according to the requirements, and the characteristics of these constituent materials are appropriately used. In addition, the manufacturing method of the separator of the present invention is not particularly limited, as long as the desired structure and material of the separator substrate 100, the material of the fluid guiding flow path, the product shape of other fuel cell components, etc. are taken into consideration, an appropriate selection is made. The preferred conditions are sufficient.
(隔板的结构及制造方法)(Structure and manufacturing method of partition)
以下参考图7作为优选的实施方式，对本发明的隔板的结构及其基本制造方法进行说明。该基本制造方法主要在实施方式1中详细描述，在实施方式2中基于实施方式1所记载的基本制造方法，着重于不同的结构与工序进行说明。在实施方式3中，基于在实施方式2中所记载的基本制造方法，着重于不同的结构与工序进行说明。Hereinafter, referring to FIG. 7 as a preferred embodiment, the structure of the separator of the present invention and the basic manufacturing method thereof will be described. This basic manufacturing method is mainly described in detail in Embodiment 1. In Embodiment 2, based on the basic manufacturing method described in Embodiment 1, the description focuses on different structures and processes. In the third embodiment, based on the basic manufacturing method described in the second embodiment, the description is focused on different structures and processes.
实施方式1 Embodiment 1
以下参考图7，说明本发明的实施方式1中的隔板及其制造方法的基本流程。另外，以下说明的实施方式1所涉及的隔板的结构和制造方法是一个参照，本发明并不限定于此。在不脱离本发明的主旨的范围内，可以根据构成部件的结构或形状、使用的材料、材料的组合成分或种类，适当地对制造工序、步骤进行追加、省略、变更。Hereinafter, referring to FIG. 7, the basic flow of the separator and its manufacturing method in Embodiment 1 of the present invention will be described. In addition, the structure and manufacturing method of the separator according to Embodiment 1 described below are a reference, and the present invention is not limited to this. Within the scope not deviating from the gist of the present invention, manufacturing processes and steps can be appropriately added, omitted, or changed in accordance with the structure or shape of the component parts, the materials used, and the combination of materials or types.
在本实施方式1中，将冷却介质流路21附着在两个具有导电性的隔板基材100之间来形成隔板主体。也就是说，隔板基材100起到形成有冷却介质流路的肋部11的底板的作用。将构成冷却介质通过的沟道的肋部11附着在隔板基材100上，因此不需要如以往那样将隔板基材100成型加工成槽形流路形状。即，可以只在将隔板基材100裁剪成隔板所需要的尺寸后，附着构成冷却介质流路的肋部11即可。另外，在本实施方式1中，如图3所示，反应气体流路附着在各个气体扩散层4、5侧，而不是隔板6、7侧，因此在上述情况下，在隔板侧不设置反应气体流路。In the first embodiment, the cooling medium flow path 21 is attached between two conductive separator base materials 100 to form a separator main body. In other words, the separator substrate 100 functions as a bottom plate on which the rib 11 of the cooling medium flow path is formed. The rib 11 constituting the channel through which the cooling medium passes is attached to the separator substrate 100, so it is not necessary to mold the separator substrate 100 into a groove-shaped flow path shape as in the past. That is, after cutting the separator base material 100 to the size required for the separator, the ribs 11 constituting the cooling medium flow path may be attached. In addition, in the first embodiment, as shown in FIG. 3, the reaction gas flow path is attached to each gas diffusion layer 4, 5 side instead of the separator 6, 7 side. Therefore, in the above case, it is not on the separator side. Set up the reaction gas flow path.
隔板需要适度的刚性和导电性。本发明的燃料电池用隔板的厚度可以是10～1,000μm。在本实施方式1中，使用厚度较薄的导电性柔性膜材作为隔板基材100来进行说明。使用电阻较低的导电性柔性膜材(10mΩ·cm 2以下)作为隔板基材100，来形成本发明的隔板。隔板基材100的厚度可以是10～50μm。如图2A所示，将位于中心的活性区域的范围内的隔板作为实施方式1的隔板，该隔板所使用的隔板基材100是通过将导电性柔性膜材切割成需要的大小所获得 的。 The separator requires moderate rigidity and conductivity. The thickness of the fuel cell separator of the present invention may be 10 to 1,000 μm. In the first embodiment, a conductive flexible film material having a thin thickness is used as the separator substrate 100 for description. A conductive flexible film material (10 mΩ·cm 2 or less) having a low electrical resistance is used as the separator substrate 100 to form the separator of the present invention. The thickness of the separator substrate 100 may be 10-50 μm. As shown in FIG. 2A, a separator located in the range of the active area in the center is used as the separator of Embodiment 1. The separator substrate 100 used in the separator is cut into a desired size by cutting a conductive flexible film material Obtained.
为了对流体引导流路的肋部11进行造型，将成为该原料的附着材料的前驱体(糊料、浆料或墨水)选择性地附着在隔板基材100上，并对其进行加热/干燥。附着材料的前驱体(糊料、浆料或墨水)的成分中存在各种各样的混合比例和种类。作为一个示例，其所包含的成分中代表性地为，导电性材料、粘合树脂、分散溶剂、各种添加剂的含碳导电性糊料。各成分可以单独使用一种，也可以混合两种以上来提高物理性质或降低价格。可以使用例如搅拌机/消泡装置作为均匀地混合上述成分的装置的一个示例。通过调整分散液的浓度，在适当的溶剂中对所需最少量的添加剂/分散剂和最大必要量的导电性材料进行搅拌、分散、混合，能获得难以在附着装置的配管或喷嘴等发生堵塞的糊状附着液(附着材料的前驱体)。In order to shape the rib 11 of the fluid guiding flow path, a precursor (paste, slurry, or ink) of the attachment material that becomes the raw material is selectively attached to the separator substrate 100 and heated/ dry. There are various mixing ratios and types in the components of the precursor (paste, slurry, or ink) of the adhesion material. As an example, the components contained therein are typically a conductive material, a binder resin, a dispersion solvent, and a carbon-containing conductive paste of various additives. Each component can be used singly, or two or more can be mixed to improve physical properties or reduce price. For example, a mixer/defoaming device can be used as an example of a device that uniformly mixes the above-mentioned ingredients. By adjusting the concentration of the dispersion, the minimum required amount of additives/dispersants and the maximum necessary amount of conductive materials are stirred, dispersed, and mixed in an appropriate solvent, so that it is difficult to block the pipes or nozzles of the attachment device. Paste attachment liquid (precursor of attachment material).
流体引导流路的附着方法可以是公知的方法，例如利用能展开涂布、印刷、点胶、喷射、转印等附着方法的装置来进行的附着方法。流路的肋部11、12是由重复进行固定的微量附着来形成的，因此期望利用自动控制装置来进行附着。可以利用包含丝网印刷机、喷墨打印机、喷涂机、辊涂机、点胶机、3D打印机、其他合适的装置的附着装置等(流路形成装置)，选择性地仅覆盖流体引导流路的肋部11、12。换言之，使用这些装置来进行局部附着，从而在基材表面对肋部11、12进行造型。此外，为了校正基材的变形并执行附着可以引入卷对卷方式的附着装置。这些自动控制附着装置有助于提高生产性。The adhesion method of the fluid guide flow path may be a known method, for example, an adhesion method using an apparatus capable of spreading adhesion methods such as coating, printing, dispensing, spraying, and transfer. Since the ribs 11 and 12 of the flow path are formed by repeated fixation of a small amount of adhesion, it is desirable to use an automatic control device for adhesion. It is possible to use attachment devices (flow path forming devices) including screen printers, inkjet printers, spraying machines, roller coaters, dispensers, 3D printers, and other suitable devices to selectively cover only the fluid guiding flow paths The ribs 11,12. In other words, these devices are used to perform partial attachment, thereby shaping the ribs 11 and 12 on the surface of the base material. In addition, in order to correct the deformation of the substrate and perform attachment, a roll-to-roll attachment device can be introduced. These automatic control attachment devices help improve productivity.
此外，也可以在经过附着工序后，进行表面处理。作为该情况下的表面处理可以是对附着的肋部11、12进行碳涂层、防水或亲水等处理，通过这些处理能提高施加到隔板基材100表面上的表面处理层和/或表面改质层105(或强化层106)与流路的肋部11、12的界面接合性和密接性，还能提高反应水的排水性。In addition, surface treatment may be performed after the adhesion process. As the surface treatment in this case, the attached ribs 11, 12 may be treated with carbon coating, water repellency, or hydrophilic treatment. These treatments can increase the surface treatment layer and/or the surface treatment layer applied to the surface of the separator substrate 100. The interface adhesion and adhesion between the surface modified layer 105 (or the reinforced layer 106) and the ribs 11 and 12 of the flow channel can also improve the drainage of the reaction water.
在本实施方式1中，流体引导流路的高度可以是例如1～500μm。由于将燃料气体流路和氧化气体流路附着在气体扩散层4、5的单侧的表面，将两个隔板基材100粘在一起的隔板主体是未指定阳极侧隔板6、阴极侧隔板7(在隔板侧未形成反应气体流路)的一种共用隔板，因此具有隔板构件的工艺管理的自由度变高，能实现装配合理化的优点。In the first embodiment, the height of the fluid guide channel may be, for example, 1 to 500 μm. Since the fuel gas flow path and the oxidizing gas flow path are attached to the surface of one side of the gas diffusion layers 4 and 5, the separator body that adheres the two separator substrates 100 together is the unspecified anode side separator 6, cathode The side partition 7 (the reaction gas flow path is not formed on the side of the partition) is a common partition. Therefore, the degree of freedom in the process management of the partition member is increased, and the assembly can be rationalized.
图7是用于说明实施方式1～3中的隔板的制造方法的示例性流程图。参考 图3～7，对本发明所涉及的隔板的制造方法进行说明。隔板的制造方法通过以下工序[1]～[8]来进行。FIG. 7 is an exemplary flowchart for explaining the method of manufacturing the separator in Embodiments 1 to 3. FIG. With reference to Figs. 3 to 7, the method of manufacturing the separator according to the present invention will be described. The manufacturing method of the separator is performed by the following steps [1] to [8].
工序[1]，形成基材，将本工序称为基材制作工序；Step [1], forming a substrate, this step is referred to as a substrate manufacturing step;
工序[2]，将基材裁剪成需要的尺寸，将本工序称为裁剪工序；Step [2], cut the substrate to the required size, and call this step the cutting step;
工序[3]，形成基材表面改质处理层，将本工序称为表面处理工序；Step [3], forming a modified treatment layer on the surface of the substrate, this step is referred to as a surface treatment step;
工序[4]，形成强化层，将本工序称为强化层形成工序；Step [4], forming a strengthening layer, this step is called a strengthening layer forming step;
工序[5]，形成冷却介质流路，将本工序称为冷却介质流路的形成工序；Step [5], forming a cooling medium flow path, this step is referred to as a cooling medium flow path forming step;
工序[6]，贴合基材，将本工序称为贴合工序；Step [6], laminating the substrate, this step is called the laminating step;
工序[7]，轧制、热处理，将本工序称为加压加热处理工序；Process [7], rolling, heat treatment, this process is called pressure heating treatment process;
工序[8]，形成反应气体流路，将本工序称为反应气体流路的形成工序。In step [8], a reaction gas flow path is formed, and this step is referred to as a reaction gas flow path forming step.
本发明的隔板的基本制造方法包含基材制作工序[1]、裁剪工序[2]、表面处理工序[3]、强化层形成工序[4]、冷却介质流路的形成工序[5]、贴合工序[6]、加压加热处理工序[7]、反应气体流路的形成工序[8]的总计8个工序。在本实施方式1中，实施包含工序[1]、[2]、[3]、[5]、[6]、[7]、[8]的总计7个工序。后述的实施方式2中，追加有形成强化层106的强化层形成工序[4]。在后述的实施方式3中，跳过强化层形成工序[4]的一部分，在反应气体流路22的形成工序[8]中，追加同时地附着强化层106和肋部12的工序。The basic manufacturing method of the separator of the present invention includes a base material production step [1], a cutting step [2], a surface treatment step [3], a strengthening layer forming step [4], a cooling medium flow path forming step [5], A total of 8 steps are the bonding step [6], the pressurizing and heating treatment step [7], and the reaction gas flow path forming step [8]. In the first embodiment, a total of 7 steps including steps [1], [2], [3], [5], [6], [7], and [8] are implemented. In the second embodiment described later, a strengthening layer forming step [4] of forming the strengthening layer 106 is added. In Embodiment 3 described later, a part of the strengthening layer forming step [4] is skipped, and a step of simultaneously attaching the strengthening layer 106 and the ribs 12 is added to the forming step [8] of the reaction gas flow path 22.
下面，对本发明的实施方式1所涉及的隔板的制造方法的流程进行说明。首先，在基材制作工序[1]中，将导电性材料、树脂组成物、强化材料组合并缠绕(混合、层叠、被膜、加压/加热、完成)，从而形成隔板基材100。接着，前进至裁剪工序[2]。Next, the flow of the manufacturing method of the separator according to the first embodiment of the present invention will be described. First, in the substrate preparation step [1], the conductive material, the resin composition, and the reinforcing material are combined and wound (mixed, laminated, coated, pressurized/heated, and completed) to form the separator substrate 100. Next, proceed to the cutting process [2].
在裁剪工序[2]中，将上述隔板基材100(例如，厚度约50μm、导电率500S/cm、热传导率1700W/mk)裁剪成需要的尺寸。执行将隔板基材100切割成大致形状的裁剪工序。另外，由于隔板基材100是非常薄的材料，因此裁剪成所需尺寸的作业会较容易。接着，前进至表面处理工序[3]。In the cutting step [2], the separator substrate 100 (for example, a thickness of about 50 μm, a conductivity of 500 S/cm, and a thermal conductivity of 1700 W/mk) is cut to a desired size. A cutting process of cutting the separator substrate 100 into a rough shape is performed. In addition, since the separator substrate 100 is a very thin material, the work of cutting to a desired size will be easier. Next, proceed to the surface treatment step [3].
在处理工序[3]中，事先对隔板基材100表面进行清洗，并在其表面实施形成表面处理层和/或表面改质层105的工序。也就是说，为了获得足够的接合性和密接性，可以进行去除存在于基材表面的异物或污染等污垢的清洗处理，然后使用与附着材料相同的材料形成镀膜(表面处理层)等，也可以形成具有该 表面处理层105中的碳组分的总计含有率从基材侧向其他材料层(例如强化层106等)侧变高的倾斜功能结构的表面处理层105，或者可以实施作为对隔板基材100的覆盖面进行改质的前处理的电晕处理、低温等离子处理、化学处理、溶剂处理、其他适当的处理等表面改质处理。例如，表面处理层105的厚度可以是1～1,000nm。表面改质层105的厚度可以是0.1～1,000nm。接着，前进至冷却介质流路的形成工序[5]。In the treatment step [3], the surface of the separator substrate 100 is cleaned in advance, and a step of forming a surface treatment layer and/or a surface modification layer 105 on the surface is performed. In other words, in order to obtain sufficient bonding and adhesion, you can perform a cleaning process to remove foreign matter or contamination on the surface of the substrate, and then use the same material as the adhesion material to form a coating (surface treatment layer), etc., also It is possible to form the surface treatment layer 105 having an inclined functional structure in which the total content rate of the carbon component in the surface treatment layer 105 increases from the substrate side to the other material layer (such as the reinforcement layer 106 etc.) side, or it can be implemented as a countermeasure The covering surface of the separator substrate 100 is subjected to surface modification treatments such as corona treatment, low-temperature plasma treatment, chemical treatment, solvent treatment, and other appropriate treatments such as pretreatment for modification. For example, the thickness of the surface treatment layer 105 may be 1 to 1,000 nm. The thickness of the surface modification layer 105 may be 0.1 to 1,000 nm. Next, proceed to the cooling medium flow path forming step [5].
在冷却介质流路的形成工序[5]中，执行仅对预先进行了表面改质处理的两个隔板基材100中的一个隔板基材100(例如第一隔板基材101)形成冷却介质流路21的工序。或者，也可以在两个隔板基材100(第一隔板基材101和第二隔板基材102)上交替地设置冷却介质流路的肋部11。在后述的实施方式中，可以在形成流体引导流路之前，执行设置强化层106的处理，但该处理是任意的，在本实施方式1中，如图3所示，示出了不设置强化层106，直接将肋部11附着于进行了表面处理的隔板基材100的示例，能获得减少隔板的厚度的效果。在上述的情况下，例如能灵活运用如图6所示的各种流路图案，兼顾厚度较薄的隔板基材100的整体框架结构来设置流体引导流路，这样能对隔板起强化效果。作为形成这些流体引导流路的附着装置的一个示例，可以采用涂布、印刷、点胶、喷射、转印等方式的流路形成装置包括丝网印刷机、喷墨打印机、点胶机、喷雾器、辊式涂布机、以及其他合理装置等的附着装置等。附着后的干燥温度与干燥速度相关，能根据使用的材料的性质选择。在将流体引导流路形成在基材表面的过程中，干燥时间越短越好。在干燥过程中使不需要的溶剂挥发而去除。接着，前进至贴合工序[6]。In the cooling medium flow path forming step [5], only one separator substrate 100 (for example, the first separator substrate 101) of the two separator substrates 100 that has been surface-modified in advance is formed The process of the cooling medium flow path 21. Alternatively, the ribs 11 of the cooling medium flow path may be alternately provided on the two separator substrates 100 (the first separator substrate 101 and the second separator substrate 102). In the embodiment described later, the process of providing the reinforcement layer 106 may be performed before the formation of the fluid guide flow path, but the process is arbitrary. In the first embodiment, as shown in FIG. 3, it is shown that the process is not provided. The reinforcing layer 106 is an example in which the rib 11 is directly attached to the surface-treated separator substrate 100, and the effect of reducing the thickness of the separator can be obtained. In the above case, for example, various flow path patterns as shown in FIG. 6 can be flexibly used, and the overall frame structure of the thin separator substrate 100 can be used to provide the fluid guiding flow path, which can strengthen the separator. effect. As an example of the attachment device that forms these fluid guiding flow paths, flow path forming devices that can adopt coating, printing, dispensing, jetting, transfer, etc. methods include screen printers, inkjet printers, dispensers, and sprayers. , Roller coater, and other reasonable devices, etc. attachment devices. The drying temperature after adhesion is related to the drying speed and can be selected according to the nature of the material used. In the process of forming the fluid guiding flow path on the surface of the substrate, the shorter the drying time, the better. In the drying process, the unnecessary solvent is volatilized and removed. Next, proceed to the bonding step [6].
作为一个示例，贴和工序[6]能在形成有流体引导流路的一个基材上使密封材料20夹持在流体引导流路的周围，贴合其他基材。重要的是边调节边进行贴合，从而将该基材与肋部11、12的界面的空气挤出，并且使附着材料不侵入成为流路的沟道部的空间。此外，在两个隔板基材100交替地设置冷却介质流路的肋部11的情况下，也能以手工方式进行贴合使肋部11恰好头尾啮合，或者也能考虑接下来的工序，使用能连续自动贴合的自动贴合装置等。接着，前进至加压加热处理工序[7]。As an example, the pasting step [6] can sandwich the sealing material 20 around the fluid guide flow path on one substrate on which the fluid guide flow path is formed, and bond the other substrates. It is important to perform bonding while adjusting, so as to squeeze out the air at the interface between the base material and the ribs 11 and 12, and to prevent the adhesion material from intruding into the space of the channel portion of the flow path. In addition, when the ribs 11 of the cooling medium flow path are alternately provided on the two separator substrates 100, it is also possible to manually attach the ribs 11 so that the ribs 11 mesh with each other, or the next process can be considered. , Use automatic laminating devices that can continuously and automatically laminate, etc. Next, proceed to the pressure heating treatment step [7].
在加压加热处理工序[7]中，用冲压机对贴合后的隔板基材100进行压接。 作为一个示例，压接方法可以是例如通过辊子加压，施加载重的加压，利用夹具或力矩扳手、松紧螺旋扣的冷冲压、热冲压的加压、以及其他方法。还能以作为一般的加热方法的辐射、传导以及对流中的某一种方式来进行。通过传导进行的加热是接触方式，通过辐射、对流进行的加热是非接触方式。在本发明的加压加热处理工序[7]中，对作为形成冷却介质流路21时的加热处理，虽然没有特别限定，但为了使热量均匀地遍布到两个基材内部以及复杂地进入其中的各个肋部11，可以使用从两个面进行的热压机以传导的接触方式施加表面压力(按压力0.01～10MPa)并进行加热。此外，通过能施加规定的面压并使其硬化的该加压加热处理，能利用包含在肋部11或强化层106的界面附近的粘结树脂中的粘接成分使界面结合，完全地去除仍然残留的水分或分散剂等成分。并且，能去除残余应力。如上所述，在该工序[7]完成时，本发明的实施方式1的隔板的基本形状完成。In the pressurizing and heating treatment step [7], the bonded separator substrate 100 is pressure-bonded with a press machine. As an example, the crimping method may be, for example, pressing by a roller, pressing with a load, pressing with a clamp or a torque wrench, cold pressing of a turnbuckle, hot pressing, and other methods. It can also be performed in one of radiation, conduction, and convection as a general heating method. Heating by conduction is a contact method, and heating by radiation and convection is a non-contact method. In the pressurization and heating treatment step [7] of the present invention, although there is no particular limitation on the heating treatment when forming the cooling medium flow path 21, in order to make the heat evenly spread into the inside of the two substrates and enter them in a complicated manner. Each of the ribs 11 can be heated by applying a surface pressure (pressing force of 0.01-10 MPa) in a conductive contact manner using a hot press from two surfaces. In addition, by the pressure and heating treatment that can apply a predetermined surface pressure and harden it, the bonding component contained in the bonding resin near the interface of the rib 11 or the reinforcing layer 106 can be used to bond the interface and completely remove it. The remaining moisture or dispersant and other ingredients. In addition, residual stress can be removed. As described above, when this step [7] is completed, the basic shape of the separator of Embodiment 1 of the present invention is completed.
接着，如图3所示，作为反应气体流路的形成工序[8]，是在工序[1]～[7]之后，通过将燃料气体流路肋部12附着在实施方式1的气体扩散层4的单面来形成阳极侧隔板6。通过将氧化气体流路肋部12附着在实施方式1的气体扩散层5的单面来形成阴极侧隔板7。Next, as shown in FIG. 3, as the reaction gas flow path formation step [8], after the steps [1] to [7], the fuel gas flow path ribs 12 are attached to the gas diffusion layer of the first embodiment. 4 to form the anode side separator 6 on one side. The cathode side separator 7 is formed by attaching the oxidizing gas flow path rib 12 to one surface of the gas diffusion layer 5 of the first embodiment.
也就是说，本发明中，作为至少附着燃料气体流路或氧化气体流路中的任何一个的基材，可以不是隔板基材100，而是气体扩散层基材，在本实施方式1中，将反应气体流路肋部12全部附着在气体扩散层4、5的表面，因此不将反应气体流路22附着在夹持了冷却介质流路21的隔板主体的外侧的表面。在该情况下，和隔板相对面的气体扩散层4、5的单侧的表面上各自附着有反应气体流路的肋部12。此外，在该情况下，并非预先在气体扩散层4、5的表面形成表面处理层和/或表面改质层105以及强化层106，而是直接将肋部12附着在气体扩散层4、5的表面。通过使附着了反应气体流路22的气体扩散层4、5的表面与对应的隔板面抵接，从而形成反应气体流路22的沟道部。另外，在本发明中，附着反应气体流路的肋部12的基材面并未特别限定，可以是气体扩散层4、5，也可以是隔板6、7。或者，也可以在隔板基材100的表面和与其相对的气体扩散层4、5的表面交替附着，使得所述两个面各自的反应气体流路肋部12不重叠。上述情况下，在隔板基材100形成表面处理层和/或表面改质层105和强化层106后附 着流路肋部11、12，在气体扩散层基材不设置表面处理层和/或表面改质层105和强化层106。That is, in the present invention, as the substrate to which at least one of the fuel gas flow path and the oxidizing gas flow path is attached, it is not necessary to use the separator substrate 100 but the gas diffusion layer substrate. In the first embodiment, Since all the reactive gas flow path ribs 12 are attached to the surfaces of the gas diffusion layers 4 and 5, the reactive gas flow path 22 is not attached to the outer surface of the separator main body sandwiching the cooling medium flow path 21. In this case, the ribs 12 of the reaction gas flow path are attached to the surfaces of the gas diffusion layers 4 and 5 on the opposite side of the separator. In this case, instead of forming the surface treatment layer and/or the surface modification layer 105 and the reinforcement layer 106 on the surfaces of the gas diffusion layers 4 and 5 in advance, the ribs 12 are directly attached to the gas diffusion layers 4 and 5 s surface. The surface of the gas diffusion layers 4 and 5 to which the reaction gas flow path 22 is attached is brought into contact with the corresponding separator surface, thereby forming the channel portion of the reaction gas flow path 22. In addition, in the present invention, the substrate surface of the rib 12 to which the reaction gas flow path is attached is not particularly limited, and may be the gas diffusion layers 4 and 5 or the separators 6 and 7. Alternatively, it is also possible to alternately adhere to the surface of the separator substrate 100 and the surfaces of the gas diffusion layers 4 and 5 opposed thereto so that the reaction gas flow path ribs 12 of the two surfaces do not overlap each other. In the above case, after forming the surface treatment layer and/or the surface modification layer 105 and the reinforcing layer 106 on the separator substrate 100, the flow channel ribs 11 and 12 are attached, and the surface treatment layer and/or the gas diffusion layer substrate are not provided Surface modification layer 105 and strengthening layer 106.
此外，构成附着在气体扩散层基材的表面的反应气体流路的肋部12的附着材料和构成冷却介质流路的肋部11的附着材料可以相同，只要是具有导电性和热传导性的材料，可以局部地不同或整个表面不同。关于实施方式1的隔板，可以适用与附着于阳极侧气体扩散层4和阴极侧气体扩散层5的反应气体流路22类似的结构、材料组成和混合比例，也可以适用不同的结构、材料组成和混合比例。In addition, the adhesion material of the rib 12 constituting the reaction gas flow path attached to the surface of the gas diffusion layer base material and the adhesion material of the rib 11 constituting the cooling medium flow path may be the same, as long as they are conductive and thermally conductive materials. , Can be different locally or different on the entire surface. Regarding the separator of the first embodiment, the structure, material composition, and mixing ratio similar to those of the reaction gas flow path 22 attached to the anode side gas diffusion layer 4 and the cathode side gas diffusion layer 5 can be applied, and different structures and materials can also be applied. Composition and mixing ratio.
图3所示的是将燃料气体流路和氧化气体流路形成于气体扩散层侧的隔板的例子。作为形成这些反应气体流路22的附着装置的一个示例，例如采用了涂布、印刷、点胶、喷射、转印方式等的流路形成装置、微量喷出装置以及其他合适的装置等。作为形成反应气体流路22时的加热处理并不特别限定，但期望是以辐射的非接触方式使用电暖炉来发射红外线来从内部进行加热。一般树脂适于3～3.5微米波长的红外线加热。根据上述的辐射，由于红外线向隔板基材100、肋部11、12或强化层106中渗透，因此具有能加热到较深部位的优点。通过该加热处理，由于包含在肋部11、12或强化层106的界面附近的粘接树脂的粘接成分使界面紧密接触，使残留的水分、分散剂等成分挥发。此外，还能去除残余应力。FIG. 3 shows an example of a separator in which a fuel gas flow path and an oxidizing gas flow path are formed on the gas diffusion layer side. As an example of the attachment device that forms these reaction gas flow paths 22, for example, flow path forming devices such as coating, printing, dispensing, spraying, and transfer methods, micro-ejection devices, and other suitable devices are used. The heating process when forming the reaction gas flow path 22 is not particularly limited, but it is desirable to use an electric heater in a non-contact method of radiation to emit infrared rays to heat from the inside. Generally, resins are suitable for infrared heating with a wavelength of 3 to 3.5 microns. According to the above-mentioned radiation, since infrared rays penetrate into the separator substrate 100, the ribs 11, 12, or the reinforcing layer 106, there is an advantage that it can be heated to a deeper portion. By this heat treatment, the bonding component of the bonding resin contained in the vicinity of the interface of the ribs 11 and 12 or the reinforcement layer 106 brings the interface into close contact, and the remaining moisture, dispersant, and other components are volatilized. In addition, residual stress can be removed.
如上所述，本发明所涉及的流体引导流路中存在反应气体流路22和冷却介质流路21两种类型。在反应气体流路22中，存在燃料气体流路(阳极)和氧化气体流路(阴极)两种。本发明的流体引导流路与在一般使用的隔板或气体扩散层中常见的基材和流路的集成气体流路不同，是构成流体引导流路的肋部11、12形成在气体扩散层4、5和隔板6、7之间这样的规格。也就是说，本发明所适用的流体引导流路并不与隔板6、7或气体扩散层4、5一体化，而是独立地位于这些基材的中间，流路肋部11、12与基材的基材不同。即，能掌握到流路肋部11、12和强化层106属于流体引导流路，表面处理层和/或表面改质层105属于隔板基材。利用实施方式2、3对反应气体流路22进行详细描述。As described above, there are two types of the fluid guide flow path according to the present invention, the reaction gas flow path 22 and the cooling medium flow path 21. In the reaction gas flow path 22, there are two types of fuel gas flow paths (anode) and oxidizing gas flow paths (cathode). The fluid guide flow path of the present invention is different from the integrated gas flow path of the substrate and the flow path commonly used in the generally used separator or gas diffusion layer, in that the ribs 11 and 12 constituting the fluid guide flow path are formed in the gas diffusion layer 4, 5 and partitions 6, 7 between such specifications. In other words, the fluid guiding flow path to which the present invention is applied is not integrated with the separators 6, 7 or the gas diffusion layers 4, 5, but is located independently in the middle of these substrates, and the flow path ribs 11, 12 are The base material of the base material is different. That is, it can be understood that the flow path ribs 11 and 12 and the reinforcement layer 106 belong to the fluid guiding flow path, and the surface treatment layer and/or the surface modification layer 105 belong to the separator base material. The reaction gas flow path 22 will be described in detail using Embodiments 2 and 3.
另外，在实施方式1中，作为两个隔板基材100，利用双方都为相同种类的导电性柔性膜材来说明，但不必是相同种类的导电性柔性膜材，若是接触电阻 较低、平坦、厚度较薄的导电性柔性膜材，则种类不同也可以。In addition, in Embodiment 1, as the two separator substrates 100, both of them are the same type of conductive flexible film material, but it is not necessary to be the same type of conductive flexible film material. If the contact resistance is low, Different types of conductive flexible film materials that are flat and thin are possible.
总之，本发明具有在一种以上的导电性柔性膜材的两个隔板基材100之间设置冷却介质流路21的特征，是能采用卷对卷方式的柔软的隔板(flexible separator：柔性隔板)。换句话说，根据实施方式1的隔板，同时具有如下功能：作为通过设置于两个隔板基材100之间的冷却介质流路21让冷却介质流过的流路作用，对位于两个单元之间的隔板6，7进行结合的作用，提供导电路径和散热路径的作用，和提高隔板主体的刚性的强化加固的作用。此外，在实施方式1中，将导电性、热传导性、不透气性优异的厚度较薄的导电性柔性膜材作为隔板基材，使用能实现反应气体不混合的不透气性的密封材料20，在气体扩散层基材表面(面向隔板侧的气体扩散层的表面)形成反应气体流路的肋部12，从而实现具有导电性、热传导性、不透气性的隔板。In short, the present invention has the feature of providing the cooling medium flow path 21 between the two separator substrates 100 of more than one conductive flexible film material, and is a flexible separator that can adopt a roll-to-roll method (flexible separator: Flexible partition). In other words, the separator according to the first embodiment also has the following function: acting as a flow path through which the cooling medium flows through the cooling medium flow path 21 provided between the two separator base materials 100, The partitions 6, 7 between the units perform the function of combining, provide conductive paths and heat dissipation paths, and strengthen the rigidity of the partition body. In addition, in the first embodiment, a thin conductive flexible film with excellent electrical conductivity, thermal conductivity, and gas impermeability is used as a separator substrate, and a gas impermeable sealing material 20 that can achieve no mixing of reactive gases is used. The ribs 12 of the reaction gas flow path are formed on the surface of the gas diffusion layer substrate (the surface of the gas diffusion layer facing the separator side), thereby realizing a separator having electrical conductivity, thermal conductivity, and gas impermeability.
如上所述，本发明的实施方式1所涉及的燃料电池用的隔板的结构和制造方法只是一个示例，当然并不限定于本说明书所记载的内容。As described above, the structure and manufacturing method of the fuel cell separator according to the first embodiment of the present invention are only an example, and of course not limited to the content described in this specification.
实施方式2 Embodiment 2
在实施方式2中，对将作为隔板基材100的导电性柔性膜材强化后的隔板进行说明。其它与实施方式1相同。本实施方式2中的隔板基材100兼用了形成有冷却介质流路的肋部11的基板以及形成有反应气体流路22的基板。In the second embodiment, a separator in which the conductive flexible film material as the separator base 100 is reinforced will be described. Others are the same as the first embodiment. The separator substrate 100 in the second embodiment uses both the substrate on which the rib 11 of the cooling medium flow path is formed and the substrate on which the reaction gas flow path 22 is formed.
本实施方式2中，通过使隔板基材100的构成材料与形成各种流体引导流路(反应气体、冷却介质)的附着材料中含有导电性材料，从而能使隔板整体具有导电性和热传导性。构成反应气体流路的肋部12可以用与构成冷却介质流路的肋部11同质的材料形成，也可以用不同质材料来形成。此外，构成表面处理层和/或表面改质层105和/或强化层106的材料可以与肋部11、12的构成材料相同，也可以一部分不同，也可以根据各种要求对混合比例进行微调整。In the second embodiment, the constituent material of the separator substrate 100 and the adhesion material forming the various fluid guide flow paths (reactive gas, cooling medium) contain a conductive material, so that the entire separator can have conductivity and Thermal conductivity. The rib 12 constituting the reaction gas flow path may be formed of the same material as the rib 11 constituting the cooling medium flow path, or may be formed of a different material. In addition, the material constituting the surface treatment layer and/or the surface modification layer 105 and/or the reinforcement layer 106 may be the same as the material of the ribs 11 and 12, or may be partly different, and the mixing ratio may be adjusted according to various requirements. Adjustment.
以下参考图7，对本发明的实施方式2中的隔板和其制造方法进行说明。另外，以下说明的实施方式2所涉及的隔板的制造方法是一个参照，本发明并不限定于此。在不脱离本发明的主旨的范围内，可以根据构成部件的结构或形状、使用的材料、材料的组合成分或种类，适当地对制造工序、步骤进行追加、省略、变更。Hereinafter, referring to FIG. 7, the separator and its manufacturing method in Embodiment 2 of the present invention will be described. In addition, the manufacturing method of the separator according to Embodiment 2 described below is a reference, and the present invention is not limited to this. Within the scope not deviating from the gist of the present invention, manufacturing processes and steps can be appropriately added, omitted, or changed in accordance with the structure or shape of the component parts, the materials used, and the combination of materials or types.
本发明的实施方式2中的隔板的制作方法是通过图7所示的下述工序[1]～ [8]来进行的。The manufacturing method of the separator in Embodiment 2 of the present invention is performed through the following steps [1] to [8] shown in FIG. 7.
如已经在实施方式1中说明的那样，本发明的隔板的制造方法包括基材制作工序[1]、裁剪工序[2]、表面处理工序[3]、强化层形成工序[4]、冷却介质流路的形成工序[5]、贴合工序[6]、加压加热处理工序[7]、反应气体流路的形成工序[8]，总计8个工序。在实施方式1中，实施工序[1]、[2]、[3]、[5]、[6]、[7]、[8]总计7个工序。在本实施方式2中，追加强化层形成工序[4]。对于与实施方式1中说明的隔板的制造工序相同的内容，省略重复说明。这里，对本发明的实施方式2的特征即强化层形成工序[4]和反应气体流路的形成工序[8]进行说明。As already explained in the first embodiment, the manufacturing method of the separator of the present invention includes a base material preparation step [1], a cutting step [2], a surface treatment step [3], a strengthening layer formation step [4], and cooling The medium flow path forming step [5], the bonding step [6], the pressurizing and heating treatment step [7], and the reaction gas flow path forming step [8] are 8 steps in total. In Embodiment 1, a total of 7 steps of steps [1], [2], [3], [5], [6], [7], and [8] are implemented. In the second embodiment, the strengthening layer forming step [4] is added. Regarding the same content as the manufacturing process of the separator described in the first embodiment, repetitive description will be omitted. Here, the characteristics of Embodiment 2 of the present invention, namely, the strengthening layer forming step [4] and the reaction gas flow path forming step [8] will be described.
下面对本发明的实施方式2的隔板的制造方法的流程进行补充说明。在本发明的实施方式2中，在表面处理工序[3]结束后，实施强化层形成工序[4]。并且，在加压加热处理工序[7]结束后，实施反应气体流路的形成工序[8]。Hereinafter, a supplementary description will be given of the flow of the manufacturing method of the separator of the second embodiment of the present invention. In the second embodiment of the present invention, after the surface treatment step [3] is completed, the strengthening layer forming step [4] is performed. In addition, after the pressurization and heating treatment step [7] is completed, the reaction gas flow path forming step [8] is performed.
如图4所示，在实施方式2的强化层形成工序[4]中，对与冷却介质流路21相对面的隔板一侧，先是涂布能提高非常薄的隔板基材刚性的强化层106，随后在其上附着冷却介质流路的肋部11。例如，强化层106的厚度可以是1～50μm。用和流路附着材料相同或不同的材料成膜的强化层106同时具有使厚度较薄的隔板基材具备刚性的作用、防止隔板基材的腐蚀的作用以及提高与流路肋部11、12的接合性和密接性的作用。除此以外，关于隔板基材100的强化性，例如能通过采用图6所示的流路图案来实现。As shown in FIG. 4, in the reinforcing layer forming step [4] of the second embodiment, the side of the separator facing the cooling medium flow path 21 is first coated to increase the rigidity of a very thin separator substrate. The layer 106 is subsequently attached to the ribs 11 of the cooling medium flow path. For example, the thickness of the reinforcement layer 106 may be 1-50 μm. The reinforced layer 106 formed with the same or different material as the flow path attachment material has the function of making the separator substrate with a thinner thickness rigid, preventing the separator substrate from corroding, and improving the connection with the flow path ribs 11 , 12 The role of bonding and adhesion. In addition, the strengthening of the separator substrate 100 can be achieved by using the flow path pattern shown in FIG. 6, for example.
如图4所示，在实施方式2的反应气体流路的形成工序[8]中，对与气体扩散层相对面的隔板基材侧，涂布非常薄的能提高隔板基材的刚性的强化层106后，在其上附着反应气体流路的肋部12。用与该附着材料相同或不同的材料成膜的强化层106同时具有使厚度较薄的隔板基材具备刚性的作用、防止隔板基材的腐蚀的作用以及提高与流路肋部11、12的接合性和密接性的作用。除此以外，关于隔板基材100的强化性，例如能通过采用图6所示的流路图案来实现。As shown in FIG. 4, in the reaction gas flow path forming step [8] of the second embodiment, the side of the separator substrate opposite to the gas diffusion layer is coated with a very thin layer to increase the rigidity of the separator substrate. After the reinforced layer 106, the ribs 12 of the reaction gas flow path are attached thereon. The reinforcing layer 106 formed with the same or different material as the adhesion material simultaneously has the function of stiffening the separator substrate with a thin thickness, preventing corrosion of the separator substrate, and improving the connection between the ribs 11, and the flow path. 12. The role of bonding and adhesion. In addition, the strengthening of the separator substrate 100 can be achieved by using the flow path pattern shown in FIG. 6, for example.
强化层106的涂布方法可以是公知的方法，例如可以包括：采用涂布、印刷、点胶、喷射、转印方式等的强化层形成装置所涵盖的成膜装置、喷涂机、点胶机、涂布器、喷墨、喷涂、辊涂装置以及其他合适的装置等。期望通过自动控制附着装置进行附着(涂布、印刷、点胶、喷射、转印)。这种自动控制附着装置有助于提高生产性。当然，也可以将形成流体引导流路的装置、形成 强化层106的装置、以及在将镀膜形成为表面处理层和/或表面改质层105的情况下使用的装置全部使用一台多功能附着装置来形成。图4所示的是在形成于两个隔板基材100的强化层106上形成有燃料气体流路的肋部12与氧化气体流路的肋部12的隔板的一个示例。The coating method of the reinforcement layer 106 may be a well-known method, for example, it may include: a film forming device, a spraying machine, and a dispenser covered by a reinforcement layer forming device using coating, printing, dispensing, spraying, transfer, etc. , Coater, inkjet, spray coating, roller coating device and other suitable devices. It is desirable to automatically control the attachment device for attachment (coating, printing, dispensing, spraying, transfer). This automatic control attachment device helps to improve productivity. Of course, it is also possible to use a single multi-function attachment for the device forming the fluid guide flow path, the device forming the strengthening layer 106, and the device used when the plating film is formed as the surface treatment layer and/or the surface modification layer 105. Device to form. FIG. 4 shows an example of a separator in which the ribs 12 of the fuel gas flow path and the ribs 12 of the oxidizing gas flow path are formed on the reinforcing layers 106 formed on the two separator base materials 100.
此外，在将反应气体流路22设置于隔板基材侧的情况下，作为反应气体流路的形成工序[8]的一环，可以通过辊涂法、喷涂法或印刷法、刷涂法等，将在反应气体流路22的整个面或局部附着亲水性涂料液、疏a水性涂料或防水涂料液。或者，也可以仅在反应气体流路22的沟道部的底部实施附着亲水性涂层液等的作业。In addition, in the case where the reaction gas flow path 22 is provided on the side of the separator substrate, as part of the reaction gas flow path formation step [8], roll coating, spray coating, printing, or brush coating can be used. For example, a hydrophilic coating liquid, a hydrophobic water-based coating, or a waterproof coating liquid will be adhered to the entire surface or part of the reaction gas flow path 22. Alternatively, the work of attaching the hydrophilic coating liquid or the like may be performed only on the bottom of the channel portion of the reaction gas flow path 22.
对于形成在阳极侧隔板6和阴极侧隔板7的反应气体流路22的平面图案，可以形成为蛇形、蛇形的旋转形状、直线形状、凹坑形状以及其他等，只要设计肋部的位置使得燃料电池具有导电性、能高效地将发电热量散热的热传导性等优异的发电特性，并且有效地将流体从各个流体的供给口引导到排出口即可。此外，只要设计反应气体流路22的图案形状，使其同时具有作为强化隔板的框架结构的作用即可。The planar pattern of the reaction gas flow path 22 formed on the anode side separator 6 and the cathode side separator 7 can be formed into a serpentine shape, a serpentine rotation shape, a linear shape, a pit shape, and others, as long as the ribs are designed The position makes the fuel cell have excellent power generation characteristics such as electrical conductivity, thermal conductivity that can efficiently dissipate power generation heat, and effectively guide fluid from the supply port of each fluid to the discharge port. In addition, it is only necessary to design the pattern shape of the reaction gas flow path 22 so that it also functions as a frame structure of the reinforcing separator.
在本实施方式2中，通过将反应气体流路的肋部12附着于隔板6、7，来形成使反应气体通过的沟道部。在本发明中，附着反应气体流路的肋部12的基材表面不作特别限定，可以是气体扩散层4、5，也可以是隔板6、7。或者，也可以在隔板基材100的表面和与其相对的气体扩散层基材的表面分别交替地附着使得反应气体流路肋部12的附着位置不重叠。In the second embodiment, by attaching the ribs 12 of the reaction gas flow path to the separators 6 and 7, a channel portion through which the reaction gas passes is formed. In the present invention, the surface of the base material of the rib 12 to which the reaction gas flow path is attached is not particularly limited, and may be the gas diffusion layers 4 and 5 or the separators 6 and 7. Alternatively, it may be alternately attached to the surface of the separator substrate 100 and the surface of the gas diffusion layer substrate opposed to it so that the attachment positions of the reaction gas flow path ribs 12 do not overlap.
总之，本发明的特征在于，由一种以上的导电性柔性膜材构成的两个隔板基材100之间设置冷却介质流路21，在夹持冷却介质流路21的隔板主体的外表面形成反应气体流路22，能采用卷对卷方式生产的柔软的隔板(flexible separator：柔性隔板)。根据实施方式1的隔板具有如下功能：作为通过设置于两个隔板基材之间的冷却介质流路21让冷却介质流过的流路作用，对位于两个单个电池单元之间的隔板6，7进行结合的作用，提供导电路径和散热路径的作用，和提高隔板主体的刚性的强化加固的作用。除此以外，通过在该隔板的至少一个侧面上形成反应气体流路22，能对阳极侧隔板6和阴极侧隔板7进行识别。在实施方式2中，将导电性、热传导性、不透气性优异的厚度较薄的导电 性柔性膜材用作为基材，使用能实现反应气体不混合的不透气性的密封材料20，在强化层106上形成冷却介质流路和反应气体流路的肋部11、12，从而能实现具有导电性、热传导性、不透气性、刚性、强化性的隔板。In short, the present invention is characterized in that a cooling medium flow path 21 is provided between two separator substrates 100 composed of one or more conductive flexible film materials, and the cooling medium flow path 21 is sandwiched outside the separator main body. The reaction gas flow path 22 is formed on the surface, and a flexible separator (flexible separator) produced by a roll-to-roll method can be used. The separator according to Embodiment 1 has a function of acting as a flow path through which the cooling medium flows through the cooling medium flow path 21 provided between two separator base materials, and acts as a flow path for the partition between two single battery cells. The plates 6 and 7 perform the function of combining, provide a conductive path and a heat dissipation path, and strengthen the rigidity of the partition body. In addition, by forming the reaction gas flow path 22 on at least one side surface of the separator, the anode side separator 6 and the cathode side separator 7 can be distinguished. In the second embodiment, a thin conductive flexible film with excellent electrical conductivity, thermal conductivity, and gas impermeability is used as a base material, and a gas impermeable sealing material 20 that can achieve no mixing of reactive gases is used to strengthen The ribs 11 and 12 of the cooling medium flow path and the reaction gas flow path are formed on the layer 106, so that a separator with electrical conductivity, thermal conductivity, gas impermeability, rigidity, and reinforcement can be realized.
根据实施方式2的隔板，可以适用与阳极侧隔板6和阴极侧隔板7类似的结构、材料组成以及混合比例，也可以适用不同的结构、材料组成以及混合比例。According to the separator of Embodiment 2, the structure, material composition, and mixing ratio similar to those of the anode-side separator 6 and the cathode-side separator 7 can be applied, and different structures, material compositions, and mixing ratios can also be applied.
本发明中，使用同一种导电性柔性膜材作为两个基材来进行说明，但也可以将阳极侧基材和阴极侧基材设为不同种基材。In the present invention, the same conductive flexible film material is used as the two substrates, but the anode-side substrate and the cathode-side substrate may be different kinds of substrates.
当然，上述的本发明的实施方式2所涉及的燃料电池用的隔板的结构和制造方法只是一个示例，并不限定于本说明书所记载的内容。Of course, the structure and manufacturing method of the fuel cell separator according to the second embodiment of the present invention described above are only an example, and are not limited to the content described in this specification.
实施方式3 Embodiment 3
在实施方式3中，进一步对将作为隔板基材的导电性柔性膜材强化后的隔板进行说明。其它与实施方式2相同。In Embodiment 3, a separator in which a conductive flexible film material as a separator base material is reinforced will be further described. Others are the same as the second embodiment.
如上所述，在反应气体流路22中存在燃料气体流路和氧化气体流路两种。与各个反应气体对应的流路形状附着于实施方式2中的隔板主体的两个面，经过该工序能区别隔板的阳极侧与阴极侧。在上述实施方式1、2中说明的隔板是设置于电池单元和单元之间的，因此在将阳极流路安装于隔板的单面时，隔板的另一面必然成为阴极。As described above, there are two types of reaction gas flow paths 22: fuel gas flow paths and oxidizing gas flow paths. The flow path shape corresponding to each reaction gas is attached to both surfaces of the separator main body in Embodiment 2, and the anode side and the cathode side of the separator can be distinguished through this process. The separators described in Embodiments 1 and 2 are provided between the battery cells and the cells. Therefore, when the anode flow path is installed on one side of the separator, the other side of the separator will inevitably become the cathode.
在实施方式3中，与实施方式2的不同点在于：在设置有实施方式2的隔板的反应气体流路22的隔板基材侧不设置强化层106，直接在基材表面形成反应气体流路22。除此以外，以与实施方式2大致相同的方式制作隔板。The third embodiment differs from the second embodiment in that the reinforcing layer 106 is not provided on the side of the separator substrate of the reactive gas flow path 22 provided with the separator of the second embodiment, and the reactive gas is directly formed on the surface of the substrate.流路22。 Flow path 22. Except for this, the separator was produced in substantially the same manner as in the second embodiment.
参考图7对本发明的实施方式3中的隔板和其制造方法进行说明。另外，以下说明的实施方式3所涉及的隔板的制造方法是一个参照，本发明并不限定于此。在不脱离本发明的主旨的范围内，可以根据构成部件的结构或形状、使用的材料、材料的组合成分或种类，适当地对制造工序、步骤进行追加、省略、变更。The separator and its manufacturing method in Embodiment 3 of the present invention will be described with reference to FIG. 7. In addition, the manufacturing method of the separator according to Embodiment 3 described below is a reference, and the present invention is not limited to this. Within the scope not deviating from the gist of the present invention, manufacturing processes and steps can be appropriately added, omitted, or changed in accordance with the structure or shape of the component parts, the materials used, and the combination of materials or types.
本发明的实施方式3中的隔板的制作方法是通过图7所示的如下工序[1]～[8]来进行的。The manufacturing method of the separator in Embodiment 3 of the present invention is performed through the following steps [1] to [8] shown in FIG. 7.
如已经在实施方式1中说明的那样，本发明的隔板的制造方法包括基材制作工序[1]、裁剪工序[2]、表面处理工序[3]、强化层形成工序[4]、冷却介质流 路的形成工序[5]、贴合工序[6]、加压加热处理工序[7]、反应气体流路的形成工序[8]，总计8个工序。在实施方式2中，实施了工序[1]、[2]、[3]、[4]、[5]、[6]、[7]、[8]总计8个工序。在本实施方式3中，跳过强化层形成工序[4]的一部分，在反应气体流路的形成工序[8]中追加同时附着强化部106A和肋部12的工序。对于与实施方式2中说明的隔板的制造工序相同的内容，省略重复说明。这里，对本发明的实施方式3的特征即反应气体流路的形成工序[8]进行说明。As already explained in the first embodiment, the manufacturing method of the separator of the present invention includes a base material preparation step [1], a cutting step [2], a surface treatment step [3], a strengthening layer formation step [4], and cooling The medium flow path forming step [5], the bonding step [6], the pressurizing and heating treatment step [7], and the reaction gas flow path forming step [8] are 8 steps in total. In Embodiment 2, a total of 8 steps of steps [1], [2], [3], [4], [5], [6], [7], and [8] are implemented. In the third embodiment, a part of the strengthening layer forming step [4] is skipped, and the step of simultaneously attaching the strengthening portion 106A and the rib 12 is added to the reaction gas flow path forming step [8]. Regarding the same content as the manufacturing process of the separator described in the second embodiment, repetitive description will be omitted. Here, the feature of Embodiment 3 of the present invention, that is, the formation step [8] of the reaction gas flow path will be described.
下面对本发明的实施方式3的隔板的制造方法的流程进行补充说明。在本发明的实施方式3中，跳过一部分强化层形成工序[4]，在加压加热处理工序[7]结束后，实施反应气体流路的形成工序[8]。Hereinafter, a supplementary description will be given of the flow of the manufacturing method of the separator of the third embodiment of the present invention. In Embodiment 3 of the present invention, a part of the strengthening layer forming step [4] is skipped, and after the pressurizing and heating treatment step [7] is completed, the reaction gas flow path forming step [8] is performed.
如图5所示，在实施方式3的强化层形成工序[4]中，在附着有冷却介质流路21的隔板基材侧设置有强化层106，在附着有反应气体流路22的隔板基材侧不设置强化层106。如图5所示，在实施方式3的反应气体流路的形成工序[8]中，以在形成反应气体流路侧的隔板面上合理地形成非常薄的能提高隔板基材100的刚性的强化部106A的方式来附着肋部12。在图5中，使用右上的局部放大图示出紧密地附着反应气体流路的肋部12的例子。使肋部12以紧密重合的方式附着的结果是可以看到必然会在基材表面的与强化层106对应的部位形成强化部106A。换言之，强化部106A与反应气体流路的肋部12同时形成。与这样的附着材料同样地进行了被膜的强化部106A除了导电性/热传导性以外，还同时具有在整个面强化厚度较薄的基材的作用以及防止隔板基材100发生腐蚀的作用。As shown in FIG. 5, in the reinforcing layer forming step [4] of the third embodiment, the reinforcing layer 106 is provided on the side of the separator substrate to which the cooling medium flow path 21 is attached, and the reactive gas flow path 22 is attached to the partition. The reinforcing layer 106 is not provided on the side of the board substrate. As shown in FIG. 5, in the reaction gas flow path formation step [8] of the third embodiment, a very thin membrane can be reasonably formed on the separator surface on the side where the reaction gas flow path is formed, which can improve the performance of the separator substrate 100. The rib 12 is attached to the rigid reinforcement 106A. In FIG. 5, an example of the rib 12 closely adhering to the reaction gas flow path is shown using the partial enlarged view on the upper right. As a result of attaching the ribs 12 in a closely overlapping manner, it can be seen that a reinforced portion 106A is inevitably formed on the surface of the base material corresponding to the reinforced layer 106. In other words, the reinforced portion 106A is formed at the same time as the rib portion 12 of the reaction gas flow path. The reinforced part 106A coated in the same manner as such an adhesion material not only has electrical conductivity and thermal conductivity, but also has a function of strengthening a thin substrate on the entire surface and a function of preventing corrosion of the separator substrate 100.
虽然重复，对在隔板基材100表面对反应气体流路22进行造型后进行的加热处理不作特别限定，期望为以辐射的非接触方式使用电暖炉来发射红外线而从内部进行加热。根据上述的辐射，由于红外线渗透在隔板基材100、肋部11、12或强化层106中，因此具有能加热到较深部位的优点。通过该加热处理，利用包含在隔板基材100、肋部11、12或强化层106的界面附近的粘接树脂的粘接成分使界面结合，使残留的水分或分散剂等成分挥发，去除残余应力。Although it is repeated, the heating treatment performed after the reaction gas flow path 22 is shaped on the surface of the separator substrate 100 is not particularly limited, and it is desirable to use an electric heater in a radiant non-contact manner to emit infrared rays and heat from the inside. According to the above-mentioned radiation, since infrared rays penetrate into the separator substrate 100, the ribs 11, 12, or the reinforcing layer 106, there is an advantage that it can be heated to a deeper portion. Through this heat treatment, the bonding component of the bonding resin contained in the vicinity of the interface between the separator substrate 100, the ribs 11, 12, or the reinforcing layer 106 is used to bond the interface, and the remaining moisture, dispersant and other components are volatilized and removed. Residual Stress.
作为形成这种反应气体流路22的附着装置的一个示例，采用涂布、印刷、点胶、喷射、转印等的流路形成装置中所包括的是：包含丝网印刷机、喷墨打印机、喷雾器、辊式涂布机、点胶机以及其他合理装置等的附着装置等。总之，本发明的特征在于：在由一种以上的导电性柔性膜材构成的两个基材之间设置 冷却介质流路21并至少在其中一个基材另一侧面上形成反应气体流路22，能采用卷对卷方式生成的柔软的隔板(flexible separator：柔性隔板)。换句话说，根据实施方式3的隔板具有如下作用：作为通过设置于两个隔板基材100之间的冷却介质流路21让冷却介质流过的流路作用，对位于两个单元之间的隔板6，7进行结合的作用，提供导电路径和散热路径的作用，和提高隔板主体的刚性的强化加固的作用。除此以外，通过在该隔板的至少一个侧面上形成反应气体流路22，能对阳极侧隔板6和阴极侧隔板7进行识别。在实施方式3中，将导电性、热传导性、不透气性优异的厚度较薄的导电性柔性膜材用作为基材，使用能实现反应气体不混合的不透气性的密封材料20，强化层106和附着在该强化层106上的冷却介质流路的肋部12对隔板进行强化，同时附着直接形成在基材的反应气体流路的肋部12和强化部106A，能以较少的工序数实现具有导电性、热传导性、不透气性、刚性、强化性的隔板。As an example of an attachment device that forms such a reactive gas flow path 22, a flow path forming device that uses coating, printing, dispensing, spraying, transfer, etc. includes: screen printers, inkjet printers, etc. , Sprayers, roller coaters, glue dispensers, and other reasonable attachment devices. In summary, the present invention is characterized in that a cooling medium flow path 21 is provided between two base materials composed of more than one conductive flexible film material, and a reactive gas flow path 22 is formed on the other side of at least one of the base materials. , Flexible separators (flexible separators) generated by roll-to-roll methods can be used. In other words, the separator according to the third embodiment has a function of acting as a flow path through which the cooling medium flows through the cooling medium flow path 21 provided between the two separator base materials 100, and acts as a flow path between the two cells. The partitions 6, 7 between the partitions have the function of combining, providing conductive paths and heat dissipation paths, and strengthening the rigidity of the partition main body. In addition, by forming the reaction gas flow path 22 on at least one side surface of the separator, the anode side separator 6 and the cathode side separator 7 can be distinguished. In the third embodiment, a thin conductive flexible film material with excellent conductivity, thermal conductivity, and gas impermeability is used as a base material, and a gas impermeable sealing material 20 that can achieve no mixing of reactive gases is used, and a reinforcing layer 106 and the ribs 12 of the cooling medium flow path attached to the reinforcing layer 106 strengthen the separator, and at the same time, the ribs 12 and the reinforced portion 106A of the reaction gas flow path formed directly on the base material are attached, so that less The number of steps to achieve a separator with electrical conductivity, thermal conductivity, air impermeability, rigidity, and reinforcement.
根据实施方式3的隔板，可以适用与阳极侧隔板6和阴极侧隔板7类似的结构、材料组成或混合比例，也可以适用不同的结构、材料组成或混合比例。According to the separator of Embodiment 3, a structure, material composition, or mixing ratio similar to that of the anode-side separator 6 and the cathode-side separator 7 can be applied, and a different structure, material composition, or mixing ratio can also be applied.
本发明中，使用同一种导电性柔性膜材作为两个基材来进行说明，但也可以将阳极侧基材和阴极侧基材设为不同种基材。In the present invention, the same conductive flexible film material is used as the two substrates, but the anode-side substrate and the cathode-side substrate may be different kinds of substrates.
当然，上述的本发明的实施方式3所涉及的燃料电池用的隔板的结构和制造方法只是一个示例，并不限定于本说明书所记载的内容。Of course, the structure and manufacturing method of the fuel cell separator according to the third embodiment of the present invention described above is only an example, and is not limited to the content described in this specification.
上述各实施方式1～3所记载的示例是分别对独立的结构进行说明。还能将各实施方式1～3适当组合来实施。The examples described in each of the above-mentioned Embodiments 1 to 3 describe independent configurations. It is also possible to implement each of Embodiments 1 to 3 in appropriate combination.
发明效果Invention effect
如上所述，本发明的实施方式1～3的隔板是由两个隔板基材100、通过附着法形成的冷却介质流路21和/或通过附着法形成的反应气体流路22构成的隔板，因此能起到以下说明的效果。As described above, the separators of the first to third embodiments of the present invention are composed of two separator base materials 100, a cooling medium flow path 21 formed by an adhesion method, and/or a reaction gas flow path 22 formed by an adhesion method The separator can therefore achieve the effects described below.
根据本发明所涉及的燃料电池用的隔板，其结构将两个使用了一种以上的导电性柔性膜材的隔板基材100贴合，并在其间设置使用具有导电性和热传导性的功能材料形成的冷却介质流路21。通过采用由电传导率和热传导性较高的隔板基材100与附着材料形成的流体引导流路，能获得导电性和热传导性稳定的隔板。此外，作为结构用途，利用形成在两个隔板基材100之间的冷却介质 流路的肋部11的强化效果，能提高隔板的比刚度。According to the fuel cell separator according to the present invention, two separator substrates 100 using more than one conductive flexible membrane material are laminated together, and a conductive and thermally conductive separator is used between them. A cooling medium flow path 21 formed of a functional material. By adopting a fluid guiding flow path formed by the separator substrate 100 with high electrical and thermal conductivity and an adhesive material, a separator with stable electrical and thermal conductivity can be obtained. In addition, for structural purposes, the reinforcement effect of the ribs 11 of the cooling medium flow path formed between the two separator base materials 100 can increase the specific rigidity of the separator.
根据本发明所涉及的燃料电池用的隔板，使用在10～100μm的范围内较薄的隔板基材100，并将流体引导流路附着在该基材上，能抑制燃料电池的单个单元的厚度、缩短燃料电池堆的层叠间隔(单元间距)，与金属隔板相比实现厚度较薄/轻量化，高功率输出体积密度以及高功率输出重量密度的燃料电池。According to the fuel cell separator of the present invention, a separator substrate 100 that is thinner in the range of 10 to 100 μm is used, and the fluid guiding flow path is attached to the substrate, thereby suppressing individual cells of the fuel cell. The thickness of the fuel cell stack is reduced, and the stacking interval (cell pitch) of the fuel cell stack is shortened. Compared with the metal separator, a fuel cell with thinner thickness/light weight, high power output volume density, and high power output weight density is realized.
根据本发明所涉及的燃料电池用的隔板，对于两个基材中的至少一个基材或两个基材，使用与肋部11、12相同或不同的材料，形成兼具强化层和框架结构的流体引导流路，能提高具有导电性、热传导性、不透气性以及耐腐蚀性的厚度较薄的隔板基材100与流路肋部的接合性和密接性，并且利用各种图案形状的流路肋部来强化隔板基材100，能提高隔板的刚性和强化性。According to the fuel cell separator according to the present invention, for at least one of the two substrates or two substrates, the same or different materials as the ribs 11 and 12 are used to form a reinforcement layer and a frame. The structure of the fluid guiding flow path can improve the adhesion and adhesion between the thin separator substrate 100 and the ribs of the flow path, which has conductivity, thermal conductivity, air impermeability, and corrosion resistance, and uses various patterns The shaped flow channel ribs strengthen the separator substrate 100, and can improve the rigidity and strengthening of the separator.
根据本发明所涉及的燃料电池用的隔板，在将反应气体流路22附着于气体扩散层4、5的表面的情况下，对两个基材进行贴合从而形成有冷却介质流路21的隔板主体能成为适用于阳极侧和阴极侧两者的共用隔板，能提高装配的自由度。According to the fuel cell separator according to the present invention, when the reaction gas flow path 22 is attached to the surface of the gas diffusion layer 4, 5, the two base materials are bonded together to form the cooling medium flow path 21 The main body of the separator can be a common separator suitable for both the anode side and the cathode side, and the freedom of assembly can be improved.
根据本发明所涉及的燃料电池用的隔板，由于将具有不透气性的柔性膜材基材作为基底，能使流过相邻的流路的反应气体不会混合，具有较高的阻气性；并且具有可有效地吸收应力的较高柔软性，通过将这种具有柔软性的隔板用于燃料电池，能缓和在发电时由电池单元内部的发热膨胀产生的MEA内部应力集中、腐蚀应力。此外，利用这种柔软性，即使在由于燃料电池使用中的外部热和外力导致发生变形的情况下，也能获得可吸收位移而不会给电池单元内部带来影响的效果。也就是说，能在组装燃料电池堆时，通过柔软地变形以防止表面压力分布不适当，使处理变得容易。通过使用本发明的隔板，能提高高活性反应环境中的热耐久性/可靠性和机械耐久性/可靠性，能提高电池寿命。According to the fuel cell separator according to the present invention, since the air-impermeable flexible membrane substrate is used as the base, the reactant gases flowing through adjacent flow paths will not be mixed, and it has a high gas barrier. And it has high flexibility that can effectively absorb stress. By using this flexible separator for fuel cells, it can alleviate the internal stress concentration and corrosion of the MEA caused by the thermal expansion inside the battery cell during power generation. stress. In addition, with this flexibility, even when the fuel cell is deformed due to external heat and force during use, the effect of absorbing displacement without affecting the inside of the battery cell can be obtained. In other words, when assembling the fuel cell stack, it can be flexibly deformed to prevent inappropriate surface pressure distribution, making handling easier. By using the separator of the present invention, thermal durability/reliability and mechanical durability/reliability in a highly active reaction environment can be improved, and battery life can be improved.
根据本发明所涉及的燃料电池用的隔板，将高导电性碳复合柔性膜材用于隔板基材100。该高导电性碳复合柔性膜材由导电性碳材料、树脂组成物以及导电性碳强化材料构成。能获得比金属隔板耐腐蚀性更强的隔板。此外，通过在隔板基材100成型时加入细石墨纤维和/或碳纳米管和/或石墨烯，从而能提高隔板基材100的刚性、导电性、热传导性以及不透气性。此外，通过使细石墨纤维和/或碳纳米管和/或石墨烯在隔板基材100面上沿垂直方向或倾斜贯通方 向进行取向，能提高与隔板基材100表面的接触电阻、界面热传导等性质。According to the fuel cell separator according to the present invention, a highly conductive carbon composite flexible membrane material is used for the separator substrate 100. The highly conductive carbon composite flexible membrane material is composed of a conductive carbon material, a resin composition, and a conductive carbon reinforcement material. A separator with stronger corrosion resistance than a metal separator can be obtained. In addition, by adding fine graphite fibers and/or carbon nanotubes and/or graphene during the molding of the separator substrate 100, the rigidity, conductivity, thermal conductivity, and gas impermeability of the separator substrate 100 can be improved. In addition, by aligning fine graphite fibers and/or carbon nanotubes and/or graphene on the surface of the separator substrate 100 in a vertical direction or an oblique penetration direction, the contact resistance and interface with the surface of the separator substrate 100 can be improved. Heat conduction and other properties.
根据本发明所涉及的燃料电池用的隔板，利用高导电性附着材料作为附着在隔板基材100上的流体引导流路的材料。包含在附着材料中的细石墨纤维、碳纳米管、石墨烯、其他材料或其组合作为第一材料，与作为第二材料的导电性树脂相互缠绕，能提高肋部11、12的导电性、机械强度、耐热强度，能赋予隔板耐热性劣化、刚性/强化性。According to the fuel cell separator according to the present invention, a highly conductive adhesive material is used as the material for the fluid guiding flow path attached to the separator base 100. The fine graphite fibers, carbon nanotubes, graphene, other materials or combinations thereof contained in the attachment material are used as the first material, and are entangled with the conductive resin as the second material, which can improve the conductivity of the ribs 11, 12, Mechanical strength and heat resistance strength can impart deterioration of heat resistance and rigidity/reinforcement of separators.
根据本发明所涉及的燃料电池用的隔板，通过并用能将各种基材卷绕成卷状的卷对卷方式和活用附着技术将流体引导流路直接附着于基材的技术，能以较低成本实现较薄、较轻、能弯曲的性质。由于附着的流体引导流路是独立于基材形成的，因此不需要用于金属隔板流路成型的模具，可获得能以较低成本且容易应对规格变更所伴随的流路设计的效果。According to the fuel cell separator of the present invention, by combining a roll-to-roll method capable of winding various substrates into a roll, and a technique that utilizes an adhesion technology to directly attach the fluid guide flow path to the substrate, it is possible to achieve Lower cost realizes thinner, lighter, and bendable properties. Since the adhering fluid guide flow path is formed independently of the base material, a mold for forming the metal separator flow path is not required, and the effect of being able to easily cope with the flow path design accompanying the specification change can be obtained at a lower cost.
根据本发明所涉及的燃料电池用的隔板，制造方法及其工序根据隔板的设计规格，由各个基材制作工序[1]、裁剪工序[2]、表面处理工序[3]、强化层形成工序[4]、冷却介质流路的形成工序[5]、贴合工序[6]、加压加热处理工序[7]、反应气体流路的形成工序[8]总计8个工序构成，由于各组件全部能使用利用附着的二维加工方法来形成，因此具有能迅速地应对规格变更所伴随的微调整的效果。According to the fuel cell separator according to the present invention, the manufacturing method and its processes are based on the design specifications of the separator, and are produced from each base material [1], cutting process [2], surface treatment process [3], and strengthening layer Formation step [4], cooling medium flow path formation step [5], bonding step [6], pressure heating treatment step [7], reaction gas flow path formation step [8], a total of 8 steps are constructed, because All components can be formed using a two-dimensional processing method using adhesion, so it has the effect of being able to quickly respond to fine adjustments associated with specification changes.
根据本发明所涉及的燃料电池用的隔板，作为流体引导流路的构成要素，由致密性碳基材料或多孔碳基材料构成的肋部11、12的附着方法使用涂布、印刷、点胶、喷射、转印方式，适用卷对卷的生产方式，因此能节省生产成本，实现效率更高的生产性。另一方面，附着材料的前驱体将一种以上的导电性材料和/或导电复合物质、一种以上粘接树脂、一种以上分散用溶剂、其他添加物、其他物质等混合来进行调制。利用该方法，能简单地调制多种附着材料，能以更低成本进行量产。According to the fuel cell separator of the present invention, as a component of the fluid guiding flow path, the method of attaching the ribs 11, 12 made of a dense carbon-based material or a porous carbon-based material uses coating, printing, and dots. Glue, spray, and transfer methods are suitable for roll-to-roll production methods, so production costs can be saved and higher productivity can be achieved. On the other hand, the precursor of the adhesion material is prepared by mixing one or more conductive materials and/or conductive composite materials, one or more adhesive resins, one or more dispersing solvents, other additives, other substances, and the like. With this method, a variety of attachment materials can be easily prepared, and mass production can be carried out at a lower cost.
根据本发明所涉及的燃料电池用的隔板，通过使用电晕处理、低温等离子处理，化学处理、溶剂处理以及其他适当的处理等作为使用了导电性柔性膜材的隔板基材100的表面改质前处理方法，能防止基材的表面腐蚀、能实现隔板基材100与流体引导流路的接合性和密接性强化。According to the fuel cell separator of the present invention, corona treatment, low-temperature plasma treatment, chemical treatment, solvent treatment, and other appropriate treatments are used as the surface of the separator substrate 100 using a conductive flexible membrane material. The pre-modification treatment method can prevent the surface of the substrate from being corroded, and can enhance the adhesion and adhesion between the separator substrate 100 and the fluid guiding flow path.
根据本发明所涉及的燃料电池用的隔板，通过在表面处理层105提供使强 化层106侧的碳组分的密度比基材侧更高的倾斜功能结构，能降低内部应力，防止基材或其他材料层的弯曲，阻止裂纹等发生，界面剥离也难以产生。According to the fuel cell separator of the present invention, by providing the surface treatment layer 105 with an inclined functional structure that makes the carbon component density of the reinforcing layer 106 higher than the base material side, the internal stress can be reduced and the base material can be prevented. Or the bending of other material layers prevents cracks from occurring, and it is difficult to produce interface peeling.
由此，根据本发明所涉及的燃料电池用的隔板，在由导电性柔性膜材构成的隔板基材的表面形成冷却介质流路21，能获得具有高导电性、高热传导性、高阻气性、耐腐蚀性的隔板。通过使用上述的厚度较薄、重量轻并且柔软的隔板来构成燃料电池单元，能获得高输出功率体积密度、高输出功率重量密度且可靠性较高的燃料电池。而且，由于适用卷对卷的生产方式，因此能实现对具有较薄、较轻、能弯曲的性质的卷状基材的处理，在低成本批量生产过程中能在生产性和成本方面进行显著地改善。Thus, according to the fuel cell separator according to the present invention, the cooling medium flow path 21 is formed on the surface of the separator substrate made of a conductive flexible membrane material, and it is possible to obtain high conductivity, high thermal conductivity, and high conductivity. A separator with gas barrier and corrosion resistance. By using the above-mentioned thinner, lighter, and flexible separator to construct a fuel cell unit, a fuel cell with high output power volume density, high output power weight density and high reliability can be obtained. Moreover, due to the application of the roll-to-roll production method, it can realize the processing of the roll-shaped substrate with thinner, lighter, and bendable properties, which can achieve significant productivity and cost in the low-cost mass production process. To improve.
以上通过若干实施方式对本发明进行了说明，但本发明不限定于这些实施方式，在不脱离本发明的主旨的范围内可进行各种变化。The present invention has been described above with several embodiments, but the present invention is not limited to these embodiments, and various changes can be made without departing from the gist of the present invention.
工业上的实用性Industrial applicability
如上所述，本发明所涉及的燃料电池用隔板能稳定地提供冷却介质和反应气体，此外，本发明所涉及的燃料电池堆能确保稳定的发电性能，因此还能适用于便携式电源、便携设备用电源、电动车用电源等用途。As described above, the fuel cell separator according to the present invention can stably supply the cooling medium and reaction gas. In addition, the fuel cell stack according to the present invention can ensure stable power generation performance, so it can also be applied to portable power supplies and portability. Power supplies for equipment, power supplies for electric vehicles, etc.
本发明的燃料电池能作为车载用燃料电池来使用。其中，除了汽车以外还可以用于无人机、飞机的蓄电池。The fuel cell of the present invention can be used as an automotive fuel cell. Among them, in addition to cars, it can also be used for batteries for drones and airplanes.
本发明并不限于上述的实施方式，在不脱离其主旨的范围内能以各种结构来实现。例如，记载于本发明的说明书的实施方式的技术特征为了解决上述问题和效果的部分或全部，能适当地进行替换或组合。The present invention is not limited to the above-mentioned embodiments, and can be implemented in various configurations within the scope not departing from the gist thereof. For example, the technical features of the embodiments described in the specification of the present invention can be appropriately substituted or combined in order to solve some or all of the above-mentioned problems and effects.

Claims (31)

  1. 一种燃料电池用的隔板，包括：A separator for fuel cells, including:
    相对设置的一对隔板基材，所述隔板基材是导电性碳复合柔性膜材；以及A pair of spacer substrates arranged oppositely, the spacer substrate being a conductive carbon composite flexible membrane material; and
    布置在所述一对隔板基材之间的冷却介质流路。A cooling medium flow path arranged between the pair of separator base materials.
  2. 如权利要求1所述的燃料电池用的隔板，其特征在于，还包括：8. The separator for a fuel cell according to claim 1, further comprising:
    布置在所述隔板基材的外侧的反应气体流路。A reaction gas flow path arranged on the outside of the separator substrate.
  3. 如权利要求1所述的燃料电池用的隔板，其特征在于，The separator for a fuel cell according to claim 1, wherein:
    还包括覆盖所述隔板基材表面的具有如下至少一种特性的表面处理层和/或表面改质层：表面耐腐蚀性、界面接合性和界面密接性。It also includes a surface treatment layer and/or a surface modification layer covering the surface of the separator substrate and having at least one of the following characteristics: surface corrosion resistance, interface adhesion, and interface adhesion.
  4. 如权利要求3所述的燃料电池用的隔板，其特征在于，The separator for a fuel cell according to claim 3, wherein:
    还包括覆盖所述表面处理层和/或表面改质层的用于提高刚性的强化层。It also includes a reinforcement layer covering the surface treatment layer and/or the surface modification layer for increasing rigidity.
  5. 如权利要求4所述的燃料电池用的隔板，其特征在于，The separator for a fuel cell according to claim 4, wherein:
    所述冷却介质流路形成在所述隔板基材上、所述表面处理层上、所述表面改质层上或所述强化层上。The cooling medium flow path is formed on the separator substrate, the surface treatment layer, the surface modification layer, or the reinforcement layer.
  6. 如权利要求5所述的燃料电池用的隔板，其特征在于，The separator for a fuel cell according to claim 5, wherein:
    还包括布置在隔板基材的外侧的反应气体流路，所述反应气体流路形成在所述隔板基材至少其中之一上、所述表面处理层上、所述表面改质层上或所述强化层上。It also includes a reactive gas flow path arranged on the outside of the separator substrate, the reactive gas flow path being formed on at least one of the separator substrate, the surface treatment layer, and the surface modification layer Or on the strengthening layer.
  7. 如权利要求1所述的燃料电池用的隔板，其特征在于，The separator for a fuel cell according to claim 1, wherein:
    所述隔板基材包括至少一种导电性材料以及至少一种树脂组成物。The separator substrate includes at least one conductive material and at least one resin composition.
  8. 如权利要求7所述的燃料电池用的隔板，其特征在于，The separator for a fuel cell according to claim 7, wherein:
    所述隔板基材还包括至少一种导电性强化材料。The separator substrate further includes at least one conductive reinforcing material.
  9. 如权利要求8所述的燃料电池用的隔板，其特征在于，The separator for a fuel cell according to claim 8, wherein:
    所述导电性强化材料包括细石墨纤维、碳纳米管和/或石墨烯。The conductive enhancement material includes fine graphite fibers, carbon nanotubes and/or graphene.
  10. 如权利要求9所述的燃料电池用的隔板，其特征在于，The separator for a fuel cell according to claim 9, wherein:
    所述导电性强化材料垂直于所述隔板基材的延伸面排列或相对于隔板基材的延伸面倾斜排列。The conductive reinforcing material is arranged perpendicular to the extension surface of the separator substrate or arranged obliquely with respect to the extension surface of the separator substrate.
  11. 如权利要求2所述的燃料电池用的隔板，其特征在于，The separator for a fuel cell according to claim 2, wherein:
    所述冷却介质流路和/反应气体流路的附着材料包括致密性的碳基材料和/ 或多孔碳基材料。The attachment material of the cooling medium flow path and/or the reaction gas flow path includes a dense carbon-based material and/or a porous carbon-based material.
  12. 如权利要求2所述的燃料电池用的隔板，其特征在于，The separator for a fuel cell according to claim 2, wherein:
    在所述反应气体流路的全部或局部区域中附着亲水性镀膜液、疏水性镀膜液或防水性镀膜液，或者仅在所述反应气体流路的沟道部的底部附着亲水性镀膜液。A hydrophilic coating solution, a hydrophobic coating solution, or a water-repellent coating solution is adhered to all or a partial area of the reaction gas flow path, or a hydrophilic coating is only adhered to the bottom of the channel portion of the reaction gas flow path liquid.
  13. 如权利要求1所述的燃料电池用的隔板，其特征在于，The separator for a fuel cell according to claim 1, wherein:
    所述隔板基材的厚度在10～200μm的范围内。The thickness of the separator substrate is in the range of 10 to 200 μm.
  14. 如权利要求3所述的燃料电池用的隔板，其特征在于，The separator for a fuel cell according to claim 3, wherein:
    所述表面处理层的厚度在1～1,000nm的范围内。The thickness of the surface treatment layer is in the range of 1 to 1,000 nm.
  15. 如权利要求4所述的燃料电池用的隔板，其特征在于，The separator for a fuel cell according to claim 4, wherein:
    所述表面改质层的厚度在0.1～1,000nm的范围内。The thickness of the surface modification layer is in the range of 0.1 to 1,000 nm.
  16. 如权利要求5所述的燃料电池用的隔板，其特征在于，The separator for a fuel cell according to claim 5, wherein:
    所述强化层的厚度在1～50μm的范围内。The thickness of the strengthening layer is in the range of 1-50 μm.
  17. 如权利要求2所述的燃料电池用的隔板，其特征在于，The separator for a fuel cell according to claim 2, wherein:
    所述冷却介质流路和/或反应气体流路的高度在1～500μm的范围内。The height of the cooling medium flow path and/or the reaction gas flow path is in the range of 1 to 500 μm.
  18. 如权利要求1所述的燃料电池用的隔板，其特征在于，The separator for a fuel cell according to claim 1, wherein:
    所述隔板的厚度在10～1,000μm的范围内。The thickness of the separator is in the range of 10 to 1,000 μm.
  19. 一种燃料电池，包括多个膜电极接合体以及多个如权利要求1-18任一项所述的隔板，每一膜电极接合体布置于相邻的隔板之间。A fuel cell comprising a plurality of membrane electrode assemblies and a plurality of separators according to any one of claims 1-18, each membrane electrode assembly being arranged between adjacent separators.
  20. 如权利要求19所述的燃料电池，其特征在于，The fuel cell according to claim 19, wherein:
    所述膜电极接合体包括催化剂涂覆膜和分别设于所述催化剂涂覆膜的第一侧和第二侧的气体扩散层。The membrane electrode assembly includes a catalyst coating film and gas diffusion layers respectively provided on a first side and a second side of the catalyst coating film.
  21. 如权利要求19所述的燃料电池，其特征在于，在所述隔板基材一侧和/或与所述隔板基材相对的气体扩散层一侧，布置有反应气体流路。The fuel cell according to claim 19, wherein a reaction gas flow path is arranged on the side of the separator substrate and/or the side of the gas diffusion layer opposite to the separator substrate.
  22. 一种燃料电池用的隔板的制造方法，其特征在于包括以下步骤：A method for manufacturing a separator for a fuel cell, which is characterized in that it comprises the following steps:
    提供为导电性碳复合柔性膜材的一对隔板基材；Provide a pair of separator substrates that are conductive carbon composite flexible membrane materials;
    在所述一对隔板基材的至少一个隔板基材的一侧附着冷却介质流路；A cooling medium flow path is attached to one side of at least one separator substrate of the pair of separator substrates;
    贴合所述一对隔板基材，其中所述冷却介质流路位于所述一对隔板基材之间。The pair of separator substrates are bonded together, wherein the cooling medium flow path is located between the pair of separator substrates.
  23. 如权利要求22所述的燃料电池用的隔板的制造方法，其特征在于，在贴合所述一对隔板基材后，还包括对所述一对隔板基材进行加压和/或加热。The method of manufacturing a separator for a fuel cell according to claim 22, wherein after bonding the pair of separator substrates, the method further comprises pressurizing the pair of separator substrates and/ Or heating.
  24. 如权利要求22所述的燃料电池用的隔板的制造方法，其特征在于，还包括在所述一对隔板基材的至少一个隔板基材的表面形成表面处理层和/或表面改质层，所述表面处理层和/或表面改质层具有如下至少一种特性：表面耐腐蚀性、界面接合性和界面密接性。The method of manufacturing a fuel cell separator according to claim 22, further comprising forming a surface treatment layer and/or surface modification on the surface of at least one separator substrate of the pair of separator substrates. The quality layer, the surface treatment layer and/or the surface modification layer has at least one of the following characteristics: surface corrosion resistance, interface adhesion, and interface adhesion.
  25. 如权利要求22所述的燃料电池用的隔板的制造方法，其特征在于，还包括在所述一对隔板基材的至少一个隔板基材的表面形成用于提高刚性的强化层。The method of manufacturing a separator for a fuel cell according to claim 22, further comprising forming a reinforcing layer for improving rigidity on the surface of at least one separator base of the pair of separator bases.
  26. 如权利要求22所述的燃料电池用的隔板的制造方法，其特征在于，还包括在所述一对隔板基材的至少一个隔板基材的非贴合侧附着反应气体流路。The method of manufacturing a separator for a fuel cell according to claim 22, further comprising attaching a reactive gas flow path to a non-bonding side of at least one separator substrate of the pair of separator substrates.
  27. 如权利要求26所述的燃料电池用的隔板的制造方法，其特征在于，还包括在所述反应气体流路的全部或局部区域涂布亲水性涂料液或防水性涂料液。The method of manufacturing a separator for a fuel cell according to claim 26, further comprising applying a hydrophilic coating liquid or a water-repellent coating liquid to all or a partial area of the reaction gas flow path.
  28. 如权利要求22所述的燃料电池用的隔板的制造方法，其特征在于，提供所述一对隔板基材的方法包括：22. The method of manufacturing a separator for a fuel cell according to claim 22, wherein the method of providing the pair of separator substrates includes:
    层叠导电性材料、导电性强化材料和树脂组成物以形成层叠体；Laminating a conductive material, a conductive reinforcing material, and a resin composition to form a laminated body;
    使用具有弹性的膜覆盖所述层叠体；Covering the laminate with an elastic film;
    加压和/或加热所述层叠体以使所述层叠体硬化。The laminated body is pressurized and/or heated to harden the laminated body.
  29. 如权利要求24所述的燃料电池用的隔板的制造方法，其特征在于，所述表面处理层的材料包括：The method of manufacturing a separator for a fuel cell according to claim 24, wherein the material of the surface treatment layer comprises:
    与构成所述冷却介质流路的肋部的材料相同的材料；或The same material as the material of the ribs constituting the cooling medium flow path; or
    碳组分的总计含有率从所述隔板基材侧向外侧变高的倾斜功能结构的材料。A material of an inclined functional structure in which the total content of carbon components increases from the side of the separator substrate toward the outside.
  30. 如权利要求25所述的燃料电池用的隔板的制造方法，其特征在于，The method of manufacturing a separator for a fuel cell according to claim 25, wherein:
    所述冷却介质流路和/或反应气体流路的附着材料包括相互缠绕的第一材料和第二材料，所述第一材料包括细碳纤维、碳纳米管、石墨烯或其组合，所述第二材料包括导电性树脂。The attachment material of the cooling medium flow path and/or the reaction gas flow path includes a first material and a second material that are entangled with each other, and the first material includes fine carbon fibers, carbon nanotubes, graphene, or a combination thereof. The second material includes conductive resin.
  31. 如权利要求25所述的燃料电池用的隔板的制造方法，其特征在于，The method of manufacturing a separator for a fuel cell according to claim 25, wherein:
    所述冷却介质流路和/或反应气体流路的附着方法包括涂布、印刷、点胶、喷射和转印。The attachment method of the cooling medium flow path and/or the reaction gas flow path includes coating, printing, glue dispensing, spraying and transfer printing.
PCT/CN2019/105090 2019-09-10 2019-09-10 Separator plate for fuel cell, manufacturing method, and fuel cell using separator plate WO2021046707A1 (en)

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